Isotactic propylene copolymers, their preparation and use

ABSTRACT

Unique copolymers comprising propylene, ethylene and/or one or more unsaturated comonomers are characterized as having: at least one, preferably more than one, of the following properties: (i)  13 C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the peaks of about equal intensity, (ii) a B-value greater than about 1.4 when the comonomer content of the copolymer is at least about 3 wt %, (iii) a skewness index, S ix , greater than about −1.20, (iv) a DSC curve with a T me  that remains essentially the same and a T max  that decreases as the amount of comonomer in the copolymer is increased, and (v) an X-ray diffraction pattern that reports more gamma-form crystals than a comparable copolymer prepared with a Ziegler-Natta catalyst These polypropylene polymers are made using a nonmetallocene, metal-centered, heteroaryl ligand catalyst. These polymers can be blended with other polymers, and are useful in the manufacture of films, sheets, foams, fibers and molded articles.

CROSS REFERENCE TO RELATED APPLICATION

This application is a division of U.S. Ser. No. 10/139,786, filed May 5,2002, now U.S. Pat. No. 6,960,635, which claims the benefit of U.S.Provisional Application No. 60/338,881, filed Nov. 6, 2001.

FIELD OF THE INVENTION

This invention relates to polypropylene. In one aspect, the inventionrelates to isotactic copolymers of propylene and at least one ofethylene and an unsaturated comonomer while in another aspect, theinvention relates to polymer blends in which at least one blendcomponent is a copolymer of propylene and at least one of ethylene andan unsaturated comonomer. In another aspect, the invention relates toprocesses for preparing copolymers of propylene and at least one ofethylene and an unsaturated comonomer and in still another aspect, theinvention relates to methods of using these copolymers and isotacticpropylene homopolymers.

BACKGROUND OF THE INVENTION

Polypropylene in its many and varied forms is a long established stapleof the polymer industry. Depending upon its form, it exhibits a numberof desirable properties including toughness (as measured by any of anumber of impact tests, e.g., notched Izod, dart drop, etc.), stiffness(as measured by any of a number of modulus tests e.g., Young's),clarity, chemical resistance and heat resistance. Often a particularcombination of properties is desired that requires a balancing ofvarious properties against one another (e.g., stiffness againsttoughness).

Crystalline polypropylene, typically a homopolymer, is used extensivelyin various moldings because it exhibits desirable mechanical (e.g.,rigidity) and chemical resistance properties. For applications thatrequire impact resistance (e.g., automobile parts, appliance facia,packaging, etc.), a copolymer of propylene and ethylene and/or one ormore α-olefins is used, or a blend of crystalline polypropylene with oneor more polymers that exhibit good impact resistance, e.g.,ethylene-propylene (EP) and/or ethylene-propylene-diene (EPDM) rubber.For applications that require toughness and/or heat resistance (e.g.,films), preferably the polypropylene has a relatively low melt flowratio (MFR) or expressed alternatively, a relatively high weight averagemolecular weight (M_(w)). For applications that require good processingcharacteristics (e.g., fibers), preferably the polypropylene has arelatively narrow polydisperity or molecular weight distribution (MWD),e.g., less than 3.5.

Crystalline polypropylene has an isotactic structure, and it is readilyproduced using a Ziegler-Natta (Z-N) or a metallocene catalyst. Whilemetallocene catalysts are effective for producing propylene homo- andcopolymers with a high isotactic index and a relatively narrow MWD, toproduce high M_(w), e.g., over 300,000, propylene homo- or copolymerseconomically with a metallocene catalyst is relatively difficult,especially in a solution process. Moreover, the industry maintains acontinuing interest in new polypropylene polymers, particularly thosefor use in high impact and fiber applications.

SUMMARY OF THE INVENTION

In a first embodiment, the invention is a copolymer of propylene,ethylene and, optionally, one or more unsaturated comonomers, e.g.,C₄₋₂₀ α-olefins, C₄₋₂₀ dienes, vinyl aromatic compounds (e.g., styrene),etc. These copolymers are characterized as comprising at least about 60weight percent (wt %) of units derived from propylene, about 0.1–35 wt %of units derived from ethylene, and 0 to about 35 wt % of units derivedfrom one or more unsaturated comonomers, with the proviso that thecombined weight percent of units derived from ethylene and theunsaturated comonomer does not exceed about 40. These copolymers arealso characterized as having at least one of the following properties:(i) ¹³C NMR peaks corresponding to a regio-error at about 14.6 and about15.7 ppm, the peaks of about equal intensity, (ii) a B-value greaterthan about 1.4 when the comonomer content, i.e., the units derived fromethylene and/or the unsaturated comonomer(s), of the copolymer is atleast about 3 wt %, (iii) a skewness index, S_(ix), greater than about−1.20, (iv) a DSC curve with a T_(me) that remains essentially the sameand a T_(max) that decreases as the amount of comonomer, i.e., the unitsderived from ethylene and/or the unsaturated comonomer(s), in thecopolymer is increased, and (v) an X-ray diffraction pattern thatreports more gamma-form crystals than a comparable copolymer preparedwith a Ziegler-Natta (Z-N) catalyst. Typically the copolymers of thisembodiment are characterized by at least two, preferably at least three,more preferably at least four, and even more preferably all five, ofthese properties.

With respect to the X-ray property of subparagraph (v) above, a“comparable” copolymer is one having the same monomer composition within10 wt %, and the same Mw within 10 wt %. For example, if an inventivepropylene/ethylene/1-hexene copolymer is 9 wt % ethylene and 1 wt %1-hexene and has a Mw of 250,000, then a comparable polymer would havefrom 8.1–9.9 wt % ethylene, 0.9–1.1 wt % 1-hexene, and a Mw between225,000 and 275,000, prepared with a Ziegler-Natta catalyst.

In a second embodiment, the invention is a copolymer of propylene andone or more unsaturated comonomers. These copolymers are characterizedin having at least about 60 wt % of the units derived from propylene,and between about 0.1 and 40 wt % the units derived from the unsaturatedcomonomer. These copolymers are also characterized as having at leastone of the following properties: (i) ¹³C NMR peaks corresponding to aregio-error at about 14.6 and about 15.7 ppm, the peaks of about equalintensity, (ii) a B-value greater than about 1.4 when the comonomercontent, i.e., the units derived from the unsaturated comonomer(s), ofthe copolymer is at least about 3 wt %, (iii) a skewness index, S_(ix),greater than about −1.20, (iv) a DSC curve with a T_(me) that remainsessentially the same and a T_(max) that decreases as the amount ofcomonomer, i.e., the units derived from the unsaturated comonomer(s), inthe copolymer is increased, and (v) an X-ray diffraction pattern thatreports more gamma-form crystals than a comparable copolymer preparedwith a Ziegler-Natta (Z-N) catalyst. Typically the copolymers of thisembodiment are characterized by at least two, preferably at least three,more preferably at least four, and even more preferably all five, ofthese properties.

In a third embodiment, the invention is a blend of two or morecopolymers in which at least one copolymer is at least one of thepropylene/ethylene and propylene/unsaturated comomoner copolymersdescribed in the first and second embodiments (individually andcollectively “P/E* copolymer”). The amount of each component in theblend can vary to convenience. The blend may contain any weight percent,based on the total weight of the blend, of either component, and theblend may be either homo- or heterophasic. If the later, the copolymerof the first or second embodiment of this invention can be either thecontinuous or discontinuous (i.e., dispersed) phase.

In a fourth embodiment, the invention is a blend of (a) at least onepropylene homopolymer, and (b) at least one other polymer, e.g. an EP orEPDM rubber. The propylene homopolymer is characterized as having ¹³CNMR peaks corresponding to a regio-error at about 14.6 and about 15.7ppm, the peaks of about equal intensity. Preferably, the propylenehomopolymer is characterized as having substantially isotactic propylenesequences, i.e., the sequences have an isotactic triad (mm) measured by¹³C NMR of greater than about 0.85.

The at least one other polymer of (b) of this fourth embodiment is anypolymer other than a P/E* copolymer. Typically and preferably, thisother polymer(s) is (are) a polyolefin such as one or more of apolyethylene, ethylene/α-olefin, butylene/α-olefin, ethylene/styrene andthe like. The blend may contain any weight percent, based on the totalweight of the blend, of either component, and the blend may be eitherhomo- or heterophasic. If the later, the propylene homopolymer can beeither the continuous or dispersed phase.

In a fifth embodiment, the invention is a process for making a P/E*copolymer, the process comprising contacting propylene and at least oneof ethylene and/or one or more unsaturated comonomers underpolymerization conditions with an activated, nonmetallocene,metal-centered, heteroaryl ligand catalyst. The process can be conductedin the solution, slurry or gas phase using conventional polymerizationconditions and equipment.

In a sixth embodiment, the invention is a solution phase process formaking a high M_(w), narrow MWD P/E* copolymer, the process comprisingcontacting propylene and at least one of ethylene and one or moreunsaturated comonomers under polymerization conditions with anactivated, nonmetallocene, metal-centered, heteroaryl ligand catalyst.

In a seventh embodiment, the invention is a series reactor process formaking a polymer blend, the blend comprising (A) a P/E* copolymer ofthis invention, and (B) a propylene homopolymer and/or a secondcopolymer. The homopolymer may or may not exhibit ¹³C NMR peakscorresponding to a regio-error at about 14.6 and about 15.7 ppm, thepeaks of about equal intensity, and the second copolymer may or may notexhibit one or more properties characterisic of the P/E* copolymers,e.g., the second copolymer may be an ethylene/α-olefin copolymer. Thereactors of this embodiment number two or more. One variation of thisprocess comprises:

-   -   1. Contacting in a first reactor (a) propylene, (b) ethylene,        and (c) a catalyst under polymerization conditions to make a P/E        copolymer, the propylene, ethylene, catalyst, and P/E copolymer        forming a reaction mass within the first reactor;    -   2. Transferring the reaction mass of the first reactor to a        second reactor;    -   3. Feeding additional propylene and/or ethylene to the second        reactor;    -   4. Contacting within the second reactor under polymerization        conditions the additional propylene and/or propylene fed to the        second reactor with the reaction mass from the first reactor to        make the polypropylene homopolymer or the second copolymer; and    -   5. Recovering the blend from the second reactor.        In one variation, one or both of the P/E copolymer and the        second copolymer is a P/E* copolymer. In another variation, if        neither the P/E copolymer nor the second copolymer is a P/E*        copolymer, then the homopolymer of (A) exhibits ¹³C NMR peaks        corresponding to a regio-error at about 14.6 and about 15.7 ppm,        the peaks of about equal intensity.

In another variation on this embodiment, the process comprises:

-   -   A. Contacting in a first reactor (i) propylene, (ii) ethylene,        and (iii) an activated, nonmetallocene, metal-centered,        heteroaryl ligand catalyst under polymerization conditions such        that at least about 50 wt % of the propylene and substantially        all of the ethylene are converted to a P/E* copolymer, the        propylene, ethylene, catalyst, and P/E* copolymer forming a        reaction mass within the first reactor;    -   B. Transferring the reaction mass of the first reactor to a        second reactor;    -   C. Optionally, feeding additional propylene to the second        reactor;    -   D. Contacting within the second reactor under polymerization        conditions the propylene fed to the second reactor with the        reaction mass from the first reactor to make the propylene        homopolymer or the second copolymer; and    -   E. Recovering the blend from the second reactor.        If (i) the only comonomers fed to the first reactor are        propylene and ethylene, (ii) substantially all of the ethylene        is consumed (i.e., converted to polymer), and (iii) only        propylene is fed to the second reactor (as unreacted propylene        from the first reactor and/or as added propylene), then only        propylene polymer containing minor, if any, amounts of ethylene        is made in the second reactor.

One interesting feature of certain of the nonmetallocene metal-centered,heteroaryl ligand catalysts used in the practice of this invention isthe ability to convert a very high percentage of ethylene monomer toP/E* copolymer in a reactor during a propylene/ethylene copolymerizationreaction. For example, with a propylene conversion of about 50% or more,the ethylene conversion may be about 90% or higher. Preferably, theethylene conversion may be higher than about 95%, more preferablygreater than about 97%, even more preferably greater than about 98%, ormost preferably greater than about 99%.

One consequence of this high ethylene conversion is that, in amultiple-reactor process, a tough, high M_(w) propylene/ethylenecopolymer can be prepared in one reactor which consumes the majority ofthe ethylene in the process. Subsequent reactors will experience agreatly reduced ethylene concentration, which can allow for theproduction of high melting point propylene homopolymer or interpolymers.Preferably, the peak crystallization temperature in a DSC cooling curveof the propylene copolymer comprising propylene and ethylene made in onereactor using a catalyst comprising a nonmetallocene, metal-centered,heteroaryl ligand catalyst is at least 10 degrees C. lower than the peakcrystallization temperature in a DSC cooling curve of the propyleneinterpolymer comprising propylene and ethylene made in a subsequentreactor. Preferably, the peak crystallization temperature is at least15, more preferably 20, most preferably 40 degrees C. lower. Preferably,at least 2 reactors are used in series, and the process is a solution,slurry, or gas-phase process, or a combination of two or more of theseprocesses. For economic reasons, a continuous process is preferred, butbatch or semi-batch processes can also be employed.

In another variation on this embodiment of the invention, the order ofthe reactors is reversed. In this arrangement, propylene homopolymer, ora propylene copolymer containing only minor amounts of ethylene, asdescribed below, can be made in the first reactor (to which the onlymonomer fed is propylene) and a copolymer of the first embodiment ofthis invention is made in the second reactor (to which is fed bothpropylene and ethylene, and optionally, one or more unsaturatedcomonomers). This arrangement can be particularly useful for gas phasereactions, but also may be used in a solution or slurry process.Irrespective of the order of the reactors, for this embodiment of theinvention it should be appreciated that, when the process is acontinuous process involving recovery of the polymer product, recoveryof the solvent (if any) and unreacted monomers, and recycle of thesolvent (if any) and unreacted monomers to the reactors, small amountsof unconverted ethylene may be present in the recycle stream. For thepurposes of this invention, when it is stated that only propylene (oronly any other particular monomer(s)) is added to any reactor in such aprocess, that small amounts of ethylene or other monomers may be presentin the recycle stream.

The reactors are operated such that the polymer made in one reactor isdifferent from the polymer made in at least one other reactor. Theseoperational differences include using (i) different weight or moleratios of propylene, ethylene and/or unsaturated comonomer, (ii)catalysts (each reactor containing a different activated,nonmetallocene, metal-centered, heteroaryl ligand catalyst, or one ormore reactors containing an activated nonmetallocene, metal-centered,heteroaryl ligand catalyst and one or more other reactors containinganother type of catalyst, e.g., a metallocene catalyst, a Ziegler-Natta(Z-N) catalyst, a constrained geometry catalyst, etc., and/or (iii)operating parameters. One or more reactors can contain more than onecatalyst, e.g., one reactor can contain both a metallocene and a Z-Ncatalyst.

In an eighth embodiment, the invention is a parallel reactor process formaking a polymer blend, the blend comprising (a) a P/E* copolymer, and(b) a propylene homopolymer and/or a second copolymer. The homopolymermay or may not exhibit ¹³C NMR peaks corresponding to a regio-error atabout 14.6 and about 15.7 ppm, the peaks of about equal intensity, andthe second copolymer may or may not exhibit one or more propertiescharacterisic of the P/E* copolymers, e.g., the second copolymer may bean ethylene/α-olefin copolymer. One variation of this process comprises:

-   -   A. Contacting in a first reactor under polymerization conditions        propylene and, optionally, one or more of ethylene and an        unsaturated comonomer to make the first polymer;    -   B. Contacting in a second reactor under polymerization        conditions propylene and, optionally, one or more of ethylene        and an unsaturated comonomer to make the second polymer;    -   C. Recovering the first polymer from the first reactor and the        second polymer from the second reactor; and    -   D. Blending the first and second polymers to form the polymer        blend;        such that at least one of the first and second polymers comprise        either (1) a P/E* copolymer, or (2) a propylene homopolymer        exhibiting ¹³C NMR peaks corresponding to a regio-error at about        14.6 and about 15.7 ppm, the peaks of about equal intensity,        made with a nonmetallocene, metal-centered, heteroaryl ligand        catalyst.

The first and second reactors are operated such that the first andsecond polymers are different from one another. These operationaldifferences include using different weight or mole ratios of propylene,ethylene and/or unsaturated comonomer, catalysts (each reactorcontaining a different nonmetallocene, metal-centered, heteroaryl ligandcatalyst, or one or more reactors containing a nonmetallocene,metal-centered, heteroaryl ligand catalyst and one or more otherreactors containing a catalyst other than a nonmetallocene,metal-centered, heteroaryl ligand catalyst), and/or operatingparameters.

The nonmetallocene, metal-centered, heteroaryl ligand catalysts used inthe practice of this invention are used in combination with one or moreactivators, e.g., an alumoxane. In certain embodiments, the metal is oneor more of hafnium and zirconium.

More specifically, in certain embodiments of the catalyst, the use of ahafnium metal has been found to be preferred as compared to a zirconiummetal for heteroaryl ligand catalysts. A broad range of ancillary ligandsubstituents may accommodate the enhanced catalytic performance. Thecatalysts in certain embodiments are compositions comprising the ligandand metal precursor, and, optionally, may additionally include anactivator, combination of activators or activator package.

The catalysts used in the practice of this invention additionallyinclude catalysts comprising ancillary ligand-hafnium complexes,ancillary ligand-zirconium complexes and optionally activators, whichcatalyze polymerization and copolymerization reactions, particularlywith monomers that are olefins, diolefins or other unsaturatedcompounds. Zirconium complexes, hafnium complexes, compositions orcompounds using the disclosed ligands are within the scope of thecatalysts useful in the practice of this invention. The metal-ligandcomplexes may be in a neutral or charged state. The ligand to metalratio may also vary, the exact ratio being dependent on the nature ofthe ligand and metal-ligand complex. The metal-ligand complex orcomplexes may take different forms, for example, they may be monomeric,dimeric or of an even higher order.

For example, suitable ligands useful in the practice of this inventionmay be broadly characterized by the following general formula:

wherein R¹ is a ring having from 4–8 atoms in the ring generallyselected from the group consisting of substituted cycloalkyl,substituted heterocycloalkyl, substituted aryl and substitutedheteroaryl, such that R¹ may be characterized by the general formula:

where Q¹ and Q⁵ are substituents on the ring other than to atom E, withE being selected from the group consisting of carbon and nitrogen andwith at least one of Q¹ or Q⁵ being bulky (defined as having at least 2atoms). Q″_(q) represents additional possible substituents on the ring,with q being 1, 2, 3, 4 or 5 and Q″ being selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof.T is a bridging group selected group consisting of —CR²R³— and —SiR²R³—with R² and R³ being independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof. J″ is generallyselected from the group consisting of heteroaryl and substitutedheteroaryl, with particular embodiments for particular reactions beingdescribed herein.

Also for example, in some embodiments, the ligands of the catalyst usedin the practice of this invention may be combined with a metal precursorcompound that may be characterized by the general formula Hf(L)_(n)where L is independently selected from the group consisting of halide(F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino,amine, hydrido, allyl, diene, seleno, phosphino, phosphine,carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates,sulphates, and combinations thereof. n is 1, 2, 3, 4, 5, or 6.

In certain aspects, it has been discovered that certain ligands complexto the metal resulting in novel complexes that can be used in thepractice of this invention. In one aspect, the 3,2 metal-ligandcomplexes that can be used in the practice of this invention may begenerally characterized by the following formula:

where M is zirconium or hafnium;

R¹ and T are defined above;

J′″ being selected from the group of substituted heteroaryls with 2atoms bonded to the metal M, at least one of those atoms being aheteroatom, and with one atom of J′″ is bonded to M via a dative bond,the other through a covalent bond; and

L¹ and L² are independently selected from the group consisting ofhalide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine,hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio,1,3-dionates, oxalates, carbonates, nitrates, sulphates, andcombinations of these radicals.

In a ninth embodiment, the invention is the use of the polypropylenehomo- and copolymers to make various fabricated articles. These polymersare particularly useful in the manufacture of such shaped articles asfilms, sheets, fibers, foams and molded articles.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the unusual comonomer distribution of apropylene/ethylene copolymer of this invention.

FIGS. 2A and 2B show a comparison of the DSC heating traces of thepropylene/ethylene (P/E) copolymer of Comparative Example 1 and the P/E*copolymer of Example 2, respectively.

FIG. 3 shows a comparison of the Tg data of a propylene/ethylene (P/E*)copolymer of this invention and a conventional Ziegler-Natta (Z-N)catalyzed P/E copolymer at equivalent crystallinity.

FIG. 4 shows a comparison of the Tg data of a P/E* copolymer of thisinvention and a conventional constrained geometry catalyst (CGC) P/Ecopolymer at the same ethylene content.

FIG. 5 shows a comparison of a TREF curve for a conventional metallocenecatalyzed P/E copolymer and a P/E* copolymer of this invention.

FIG. 6 shows the ¹³C NMR spectrum of the propylene homopolymer productof Example 7, prepared using Catalyst G. This spectrum shows the highdegree of isotacticity of the product.

FIG. 7 shows the ¹³C NMR Spectrum of the propylene homopolymer productof Example 8, prepared using Catalyst H. This spectrum is shown at anexpanded Y-axis scale relative to FIG. 6 in order to more clearly showthe regio-error peaks.

FIG. 8 shows the ¹³C NMR Spectrum of the P/E* copolymer product ofExample 2 prepared using Catalyst G.

FIG. 9 shows the ¹³C NMR Spectrum of the P/E copolymer product ofComparative Example 1 prepared using metallocene Catalyst Edemonstrating the absence of regio-error peaks in the region around 15ppm.

FIG. 10 shows a haze versus mole percent ethylene comparison of aconventional metallocene catalyzed P/E copolymer and a P/E* copolymer ofthis invention.

FIG. 11 shows a haze versus Tmax comparison of a conventionalmetallocene catalyzed P/E copolymer and a P/E* copolymer of thisinvention.

FIG. 12 shows an Eflex versus Tmax comparison of a conventionalmetallocene catalyzed P/E copolymer and a P/E* copolymer of thisinvention.

FIG. 13 shows an Eflex versus mole percent ethylene comparison of aconventional metallocene catalyzed P/E copolymer and a P/E* copolymer ofthis invention.

FIG. 14 is a bar graph comparing the elasticity of unstretched P/E*copolymers of this invention against various conventional unstretchedthermoplastic elastomers.

FIG. 15 is a bar graph comparing the elasticity of pre-stretched P/E*copolymers of this invention against various conventional pre-stretchedthermoplastic elastomers.

FIG. 16 shows a comparison of the haze of a blown film made from a P/E*copolymer of this invention against the haze of blown films made fromZ-N catalyzed conventional P/E copolymers.

FIG. 17 shows a comparison of the MD-tear of a blown film made from aP/E* copolymer of this invention against the MD-tear of blown films madefrom Z-N catalyzed conventional P/E copolymers.

FIG. 18 shows a comparison of the dart of a blown film made from a P/E*copolymer of this invention against the dart of blown films made fromZ-N catalyzed conventional P/E copolymers.

FIG. 19 shows a comparison of the hot tack behavior of a blown film madefrom a P/E* copolymer of this invention against the hot tack behavior ofblown films made from Z-N catalyzed conventional P/E copolymers.

FIG. 20 shows a comparison of the heat sealing behavior of a blown filmmade from a P/E* copolymer of this invention against the heat sealingbehavior of blown films made from Z-N catalyzed conventional P/Ecopolymers.

FIGS. 21A - 21J show the chemical structures of various catalysts.

FIG. 22 shows a comparison of the skewness index for the P/E* copolymerof this invention and several P/E copolymers known in the art.

FIGS. 23A and 23B shows the DSC heating and cooling traces of thepropylene homopolymer of Example 8, prepared using Catalyst H.

FIG. 24 compares the melting endotherms of Samples 8 and 22a of Example18.

FIG. 25 demonstrates the shift in peak melting temperature towards lowertemperature for samples of the copolymers of this invention of Example18.

FIG. 26 is a plot of the temperature at which approximately 1 percentcrystallinity remains in DSC samples of Example 18.

FIG. 27 shows the variance relative to the first moment of the meltingendotherm as a function of the heat of melting of various samples ofExample 18.

FIG. 28 shows the maximum heat flow normalized by the heat of melting asa function of the heat of melting for various samples of Example 18.

FIG. 29 illustrates that the rate at which the last portion ofcrystallinity disappears in the inventive polymers is significantlylower than for metallocene polymers.

FIG. 30 shows a comparison of the CD-tear of a blown film made from aP/E* copolymer of this invention against the CD-tear of blown films madefrom Z-N catalyzed conventional P/E copolymers.

FIG. 31 shows a comparison of the Gloss-45 of a blown film made from aP/E* copolymer of this invention against the MD-tear of blown films madefrom Z-N catalyzed conventional P/E copolymers.

FIG. 32 shows the MD-tear for various blown films made from a blend ofP/E* copolymer of this invention and various other P/E copolymers.

FIG. 33 shows the CD-tear for various blown films made from a blend ofP/E* copolymer of this invention and various other P/E copolymers.

FIG. 34 shows the Dart Impact for various blown films made from a blendof P/E* copolymer of this invention and various other P/E copolymers.

FIG. 35 shows the CD-Elongation percent for various blown films madefrom a blend of P/E* copolymer of this invention and various other P/Ecopolymers.

FIG. 36 shows the CD-Ultimate in psi for various blown films made from ablend of P/E* copolymer of this invention and various other P/Ecopolymers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Molecular Weight

The weight average molecular weight (Mw) of the polymers of thisinvention can vary widely, but typically it is between about 30,000 and1,000,000 (with the understanding that the only limit on the minimum orthe maximum M_(w) is that set by practical considerations). Preferablythe minimun Mw is about 50,000, more preferably about 75,000 and evenmore preferably about 100,000. “High molecular weight”, “high weightaverage molecular weight”, “high Mw” and similar terms mean a weightaverage molecular weight of at least about 250,000, preferably of atleast about 300,000 and more preferably 350,000, and more preferably atleast about 400,000.

Polydispersity

The polydispersity of the polymers of this invention is typicallybetween about 2 and about 6. “Narrow polydisperity”, “narrow molecularweight distribution”, “narrow MWD” and similar terms mean a ratio(M_(w)/M_(n)) of weight average molecular weight (M_(w)) to numberaverage molecular weight (M_(n)) of less than about 3.5, preferably lessthan about 3.0, more preferably less than about 2.8, more preferablyless than about 2.5, and most preferably less than about 2.3. Polymersfor use in fiber and extrusion coating applications typically have anarrow polydispersity.

Blends comprising the inventive polymers may have a higherpolydispersity, depending on the molecular weight of the othercomponents of the blend. In particular, blends produced utilizing any ofthe multiple reactor processes disclosed in the present invention mayhave a broad range of polydispersities, from as low as about 2 to ashigh as 100 or more. Preferably, the M_(w)/M_(n) of such blends isbetween about 2 and about 50, more preferably between about 2 and about20, most preferably between about 2 and about 10.

Gel Permeation Chromatography

Molecular weight distribution of the polymers is determined using gelpermeation chromatography (GPC) on a Polymer Laboratories PL-GPC-220high temperature chromatographic unit equipped with four linear mixedbed columns (Polymer Laboratories (20-micron particle size)). The oventemperature is at 160° C. with the autosampler hot zone at 160° C. andthe warm zone at 145° C. The solvent is 1,2,4-trichlorobenzenecontaining 200 ppm 2,6-di-t-butyl-4-methylphenol. The flow rate is 1.0milliliter/minute and the injection size is 100 microliters. About 0.2%by weight solutions of the samples are prepared for injection bydissolving the sample in nitrogen purged 1,2,4-trichlorobenzenecontaining 200 ppm 2,6-di-t-butyl-4-methylphenol for 2.5 hrs at 160° C.with gentle mixing.

The molecular weight determination is deduced by using ten narrowmolecular weight distribution polystyrene standards (from PolymerLaboratories, EasiCal PSI ranging from 580–7,500,000 g/mole) inconjunction with their elution volumes. The equivalent polypropylenemolecular weights are determined by using appropriate Mark-Houwinkcoefficients for polypropylene (as described by Th. G. Scholte, N. L. J.Meijerink, H. M. Schoffeleers, and A. M. G. Brands, J. Appl. Polym.Sci., 29, 3763–3782 (1984)) and polystyrene (as described by E. P.Otocka, R. J. Roe, N. Y. Hellman, P. M. Muglia, Macromolecules, 4, 507(1971)) in the Mark-Houwink equation:{N}=KM^(a)where K_(pp)=1.90E-04, a_(pp)=0.725 and K_(ps)=1.26E-04, a_(ps)=0.702.Differential Scanning Calorimetry

Differential scanning calorimetry (DSC) is a common technique that canbe used to examine the melting and crystallization of semi-crystallinepolymers. General principles of DSC measurements and applications of DSCto studying semi-crystalline polymers are described in standard texts(e.g., E. A. Turi, ed., Thermal Characterization of Polymeric Materials,Academic Press, 1981). Certain of the copolymers of this invention arecharacterized by a DSC curve with a T_(me) that remains essentially thesame and a T_(max) that decreases as the amount of unsaturated comonomerin the copolymer is increased. T_(me) means the temperature at which themelting ends. T_(max) means the peak melting temperature.

Differential Scanning Calorimetry (DSC) analysis is determined using amodel Q1000 DSC from TA Instruments, Inc. Calibration of the DSC is doneas follows. First, a baseline is obtained by running the DSC from −90°C. to 290° C. without any sample in the aluminum DSC pan. Then 7milligrams of a fresh indium sample is analyzed by heating the sample to180° C., cooling the sample to 140° C. at a cooling rate of 10° C./minfollowed by keeping the sample isothermally at 140° C. for 1 minute,followed by heating the sample from 140° C. to 180° C. at a heating rateof 10° C./min. The heat of fusion and the onset of melting of the indiumsample are determined and checked to be within 0.5° C. from 156.6° C.for the onset of melting and within 0.5 J/g from 28.71 J/g for the heatof fusion. Then deionized water is analyzed by cooling a small drop offresh sample in the DSC pan from 25° C. to −30° C. at a cooling rate of10° C./min. The sample is kept isothermally at −30° C. for 2 minutes andheated to 30° C. at a heating rate of 10° C./min. The onset of meltingis determined and checked to be within 0.5° C. from 0° C.

The polypropylene samples are pressed into a thin film at a temperatureof 190° C. About 5 to 8 mg of sample is weighed out and placed in theDSC pan. The lid is crimped on the pan to ensure a closed atmosphere.The sample pan is placed in the DSC cell and the heated at a high rateof about 100° C./min to a temperature of about 30° C. above the melttemperature. The sample is kept at this temperature for about 3 minutes.Then the sample is cooled at a rate of 10° C./min to −40° C., and keptisothermally at that temperature for 3 minutes. Consequently the sampleis heated at a rate of 10° C./min until complete melting. The resultingenthalpy curves are analyzed for peak melt temperature, onset and peakcrystallization temperatures, heat of fusion and heat ofcrystallization, T_(me), and any other DSC analyses of interest.

B-Value

“High B-value” and similar terms mean the ethylene units of a copolymerof propylene and ethylene, or a copolymer of propylene, ethylene and atleast one unsaturated comononomer, is distributed across the polymerchain in a nonrandom manner. B-values range from 0 to 2 with 1designating a perfectly random distribution of comonomer units. Thehigher the B-value, the more alternating the comonomer distribution inthe copolymer. The lower the B-value, the more blocky or clustered thecomonomer distribution in the copolymer. The high B-values of thepolymers of this invention are typically at least about 1.3, preferablyat least about 1.4, more preferably at least about 1.5 and mostpreferably at least about 1.7. The B-value is calculated as follows.

B is defined for a propylene/ethylene copolymer as:

$B = \frac{f( {{EP} + {PE}} )}{2 \cdot F_{E} \cdot F_{P}}$where f(EP+PE)=the sum of the EP and PE diad fractions; and Fe andFp=the mole fraction of ethylene and propylene in the copolymer,respectively. B-values can be calculated for other copolymers in ananalogous manner by assignment of the respective copolymer diads. Forexample, calculation of the B-value for a propylene/1-octene copolymeruses the following equation:

$B = \frac{f( {{OP} + {PO}} )}{2 \cdot F_{O} \cdot F_{P}}$

For propylene polymers made with a metallocene catalyst, the B-valuesare typically between 1.1 and 1.3. For propylene polymers made with aconstrained geometry catalyst, the B-values are typically between 0.9and 1.0. In contrast, the B-values of the propylene polymers of thisinvention, typically made with an activated nonmetallocene,metal-centered, heteroaryl ligand catalyst, are above about 1.4,typcially between about 1.5 and about 1.85. In turn, this means that forany propylene-ethylene copolymer of this invention, not only is thepropylene block length relatively short for a given percentage ofethylene but very little, if any, long sequences of 3 or more sequentialethylene insertions are present in the copolymer, unless the ethylenecontent of the polymer is very high. FIG. 1 and the data of thefollowing tables are illustrative. The catalysts are activatednonmetallocene, metal-centered, heteroaryl ligand catalysts, and thesemade polymers of this invention. The Catalyst E is a metallocenecatalyst, and it did not make the polymers of this invention.Interestingly, the B-values of the propylene polymers of this inventionremained high even for polymers with relatively large amounts, e.g., >30mole %, ethylene.

TABLE A B-Values of Selected Propylene Polymers Regio-errors 14–16 ppmMFR Density Ethylene (mole %) Tmax Cryst. (%) Tg Number Description(g/10 min) (kg/dm 3#) (mol %) (average of two) B (° C.) (from Hf) (° C.)A-1 P/E* via 25.8 0.8864 10.6 0.00 1.40 104.7 37.3 −20.9 Catalyst I A-2HPP via 1.9 0.8995 0.0 1.35 None 139.5 48.7 −6.9 Catalyst G A-3 P/E* via1.7 0.8740 11.8 0.24 1.67 63.3 24.4 −23.6 Catalyst G A-4 P/E* via 1.50.8703 12.9 0.32 1.66 57.7 21.9 −24.5 Catalyst G A-5 HPP via 2.5 0.90210.0 1.18 none 143.5 61.4 −6.0 Catalyst H A-6 P/E* via 1.9 0.8928 4.30.57 1.77 120.6 48.3 −13.8 Catalyst H A-7 P/E* via 2.2 0.8850 8.2 0.471.71 96.0 40.5 −19.3 Catalyst H A-8 P/E* via 2.3 0.8741 11.8 0.34 1.7967.9 27.4 −23.7 Catalyst H A-9 P/E* via 2 0.8648 15.8 0.24 1.67 53.710.5 −27.6 Catalyst H A-10 P/E* via 2.0 0.8581 18.6 0.18 1.70 none 2.6−29.9 Catalyst HCatalyst I isdimethyleamidoborane-bis-η⁵-(2-methyl-4-napthylinden-1-yl)zirconiumη⁴-1,4,-dipheny-1,3-butadiene. HPP means polypropylene homopolymer.

TABLE B B-Values of Selected Propylene/Ethylene Copolymers Regio-errors14–16 ppm (mole MFR Density Ethylene %) (average of Tmax Cryst. (%) TgNumber Description (g/10 min) (kg/dm3) (mol %) two) B (° C.) (from Hf)(° C.) B-1 P/E* via Catalyst H 1.8 1.6 0.37 1.78 138.2 53.9 −8.1 B-2P/E* via Catalyst H 1.7 7.7 0.38 1.66 105.6 38.9 −18.5 B-3 P/E* viaCatalyst H 27.0 7.8 0.41 1.61 107.7 39.6 −18.2 B-4 P/E* via Catalyst H1.9 12.3 0.31 1.58 74.7 30.7 −22.5 B-5 P/E* via Catalyst H 25.5 14.80.21 1.67 90.6 31.2 −22.9 B-6 P/E* via Catalyst H 25.7 12.4 0.31 1.6167.4 20.8 −26.8 B-7 P/E* via Catalyst H 52.2 14.7 0.30 1.60 78.1 19.9−25.9 B-8 P/E* via Catalyst H 27.0 33.7 0.00 1.67 none 0.0 −39.2 B-9P/E* via Catalyst H 76.0 31.3 0.00 1.67 none 0.0 −39.2 B-10 P/E* viaCatalyst J 12.0 0.25 1.61 72.4 33.2 −22.8 B-11 P/E* via Catalyst J 8.90.37 1.63 91.4 40.1 −19.8 B-12 P/E* via Catalyst J 8.5 0.44 1.68 101.738.7 −20.0 B-13 P/E* via Catalyst J 7.6 0.47 1.68 107.6 43.2 −18.8 B-14P/E* via Catalyst J 7.6 0.35 1.64 106.2 42.4 −18.5 B-15 P/E* viaCatalyst J 8.6 0.33 1.64 104.4 41.0 −19.5 B-16 P/E* via Catalyst J 9.60.35 1.65 85.5 38.1 −20.6 B-17 P/E* via Catalyst J 8.6 0.37 1.63 104.141.8 −19.6 B-18 P/E* via Catalyst J 8.6 0.34 1.62 90.8 40.8 −19.6 B-19P/E* via Catalyst J 8.6 0.40 1.58 93.3 41.9 −19.2

The novel processes disclosed of this invention can be used to producepropylene interpolymers of ethylene and optionally C₄–C₂₀ alpha-olefinshaving a relatively broad melting point in a DSC heating curve. Whilenot wishing to be held to any particular theory of operation, it isbelieved that the high B values for the novel propylene/ethyleneinterpolymers and the process for their manufacture lead to an ethylenedistribution within the polymer chains that leads to a broad meltingbehavior. In FIGS. 2A and 2B, for example, a relatively narrow meltingpeak is observed for a propylene/ethylene copolymer prepared using ametallocene as a comparative example (Comparative Example 1), while themelting peak for a similar copolymer of propylene and ethylene preparedaccording to the teachings herein exhibits a broad melting point. Suchbroad melting behavior is useful in applications requiring, for example,a relatively low heat seal initiation temperature, or a broad hot tackand/or heat seal window.

Thermal Properties

FIGS. 3 and 4 further illustrate the thermal properties of the propylenepolymers of this invention. FIG. 3 illustrates that the propylenepolymers of this invention have a higher glass transition temperaure(Tg) than do comparable metallocene-catalysed propylene polymers at aequivalent crystallinity. This means that the P/E* copolymers of thisinvention are likely to exhibit better creep resistance thanconventional metallocene-catalyzed propylene copolymers. Moreover, theT_(max) data of Table A shows that the P/E* copolymers of this inventionhave a lower melting point at the same crystallinity as ametallocene-catalyzed propylene copolymer. This, in turn, means that thepropylene polymers of this invention are likely to process better (e.g.,require less heating) than conventional metallocene-catalyzed propylenepolymers.

FIG. 4 illustrates that the propylene polymers of this invention alsohave a lower Tg at an equivalent ethylene content than a propylenepolymer made with a constrained geometry catalyst (CGC) and this, inturn, means that the inventive propylene polymers are likely to exhibitbetter low temperature toughness than the CGC propylene polymers makingthe inventive polymers attractive candidates for food packagingapplications.

Temperature-Rising Elution Fractionation

The determination of crystallizable sequence length distribution can beaccomplished on a preparative scale by temperature-rising elutionfractionation (TREF). The relative mass of individual fractions can beused as a basis for estimating a more continuous distribution. L. Wild,et al., Journal of Polymer Science: Polymer. Physics Ed., 20, 441(1982), scaled down the sample size and added a mass detector to producea continuous representation of the distribution as a function of elutiontemperature. This scaled down version, analytical temperature-risingelution fractionation (ATREF), is not concerned with the actualisolation of fractions, but with more accuractely determining the weightdistribution of fractions.

While TREF was originally applied to copolymers of ethylene and higherα-olefins, it can also be used for the analysis of copolymers ofpropylene with ethylene (or higher α-olefins). The analysis ofcopolymers of propylene requires higher temperatures for the dissolutionand crystallization of pure, isotactic polypropylene, but most of thecopolymerization products of interest elute at similar temperatures asobserved for copolymers of ethylene. The following table is a summary ofconditions used for the analysis of copolymers of propylene. Except asnoted the conditions for TREF are consistent with those of Wild, et al.,ibid, and Hazlitt, Journal of Applied Polymer Science: Appl. Polym.Symp.,45, 25(1990).

TABLE C Parameters Used for TREF Parameter Explanation Column typeStainless steel shot with 1.5 cc interstitial volume and size Massdetector Single beam infrared detector at 2920 cm⁻¹ Injection  150° C.temperature Temperature control GC oven device Solvent1,2,4-trichlorobenzene Concentration  0.1 to 0.3% (weight/weight)Cooling Rate 1  140° C. to 120° C. @ −6.0° C./min. Cooling Rate 2  120°C. to 44.5° C. @ −0.1° C./min. Cooling Rate 3 44.5° C. to 20° C. @ −0.3°C./min. Heating Rate   20° C. to 140° C. @ 1.8° C./min. Data acquisitionrate 12/min.

The data obtained from TREF are expressed as a normalized plot of weightfraction as a function of elution temperature. The separation mechanismis analogous to that of copolymers of ethylene, whereby the molarcontent of the crystallizable component (ethylene) is the primary factorthat determines the elution temperature. In the case of copolymers ofpropylene, it is the molar content of isotactic propylene units thatprimarily determines the elution temperature. FIG. 5 is a representationof the typical type of distribution one would expect for apropylene/ethylene copolymer made with a metallocene polymer and anexample of the current invention.

The shape of the metallocene curve in FIG. 5 is typical for ahomogeneous copolymer. The shape arises from the inherent, randomincorporation of comonomer. A prominent characteristic of the shape ofthe curve is the tailing at lower elution temperature compared to thesharpness or steepness of the curve at the higher elution temperatures.A statistic that reflects this type of assymetry is skewness. Equation 1mathematically represents the skewness index, S_(ix), as a measure ofthis asymmetry.

$\begin{matrix}{S_{ix} = {\frac{\sqrt[3]{\sum\limits^{\;}\;{w_{i}*( {T_{i} - T_{Max}} )^{3}}}}{\sqrt{{\sum{w_{i}*( {T_{i} - T_{Max}} )^{2}}}\mspace{11mu}}}.}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

The value, T_(Max), is defined as the temperature of the largest weightfraction eluting between 50 and 90° C. in the TREF curve. T_(i) andw_(i) are the elution temperature and weight fraction respectively of anabitrary, i^(th) fraction in the TREF distribution. The distributionshave been normalized (the sum of the w_(i) equals 100%) with respect tothe total area of the curve eluting above 30° C. Thus, the indexreflects only the shape of the crystallized polymer and anyuncrystallized polymer (polymer still in solution at or below 30° C.)has been omitted from the calculation shown in Equation 1.

Polymer Definitions and Descriptions

“Polymer” means a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, although it is often usedinterchangeably with “interpolymer” to refer to polymers made from threeor more different types of monomers or comonomers), terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike. The terms “monomer” or “comonomer” are used interchangeably, andthey refer to any compound with a polymerizable moiety which is added toa reactor in order to produce a polymer. In those instances in which apolymer is described as comprising one or more monomers, e.g., a polymercomprising propylene and ethylene, the polymer, of course, comprisesunits derived from the monomers, e.g., —CH₂—CH₂—, and not the monomeritself, e.g., CH₂═CH₂.

“Metallocene-catalyzed polymer” or similar term means any polymer thatis made in the presence of a metallocene catalyst. “Constrained geometrycatalyst catalyzed polymer”, “CGC-catalyzed polymer” or similar termmeans any polymer that is made in the presence of a constrained geometrycatalyst. “Ziegler-Natta-catalyzed polymer”, “Z-N-catalyzed polymer” orsimilar term means any polymer that is made in the presence of aZiegler-Natta catalyst. “Metallocene” means a metal-containing compoundhaving at least one substituted or unsubstituted cyclopentadienyl groupbound to the metal. “Constrained geometry catalyst” or “CGC” as hereused has the same meaning as this term is defined and described in U.S.Pat. Nos. 5,272,236 and 5,278,272.

“Random copolymer” means a copolymer in which the monomer is randomlydistributed across the polymer chain. “Impact copolymer” means two ormore polymers in which one polymer is dispersed in the other polymer,typically one polymer comprising a matrix phase and the other polymercomprising an elastomer phase. The matrix polymer is typically acrystalline polymer, e.g., polypropylene homopolymer or copolymer, andthe polymer comprising the elastomer phase is typically a rubber orelastomer, e.g., an EP or an EPDM rubber. The polymer that forms theelastomer phase typically comprises between about 5 and about 50,preferably between about 10 and 45 and more preferably between about 10and 40, weight percent of the impact polymer.

“Propylene homopolymer” and similar terms mean a polymer consistingsolely or essentially all of units derived from propylene.“Polypropylene copolymer” and similar terms mean a polymer comprisingunits derived from propylene and ethylene and/or one or more unsaturatedcomonomers. The term “copolymer” includes terpolymers, tetrapolymers,etc.

The unsaturated comonomers used in the practice of this inventioninclude, C₄₋₂₀ α-olefins, especially C₄₋₁₂ α-olefins such as 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,1-dodecene and the like; C₄₋₂₀ diolefins, preferably 1,3-butadiene,1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) anddicyclopentadiene; C₈₋₄₀ vinyl aromatic compounds including sytrene, o-,m-, and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnapthalene;and halogen-substituted C₈₋₄₀ vinyl aromatic compounds such aschlorostyrene and fluorostyrene. For purposes of this invention,ethylene is not included in the definition of unsaturated comonomers.

The propylene copolymers of this invention typically comprise unitsderived from propylene in an amount of at least about 60, preferably atleast about 80 and more preferably at least about 85, wt % of thecopolymer. The typical amount of units derived from ethylene inpropylene/ethylene copolymers is at least about 0.1, preferably at leastabout 1 and more preferably at least about 5 wt %, and the maximumamount of units derived from ethylene present in these copolymers istypically not in excess of about 35, preferably not in excess of about30 and more preferably not in excess of about 20, wt % of the copolymer.The amount of units derived from the unsaturated comonomer(s), ifpresent, is typically at least about 0.01, preferably at least about 1and more preferably at least about 5, wt %, and the typical maximumamount of units derived from the unsaturated comonomer(s) typically doesnot exceed about 35, preferably it does not exceed about 30 and morepreferably it does not exceed about 20, wt % of the copolymer. Thecombined total of units derived from ethylene and any unsaturatedcomonomer typically does not exceed about 40, preferably it does notexceed about 30 and more preferably it does not exceed about 20, wt % ofthe copolymer.

The copolymers of this invention comprising propylene and one or moreunsaturated comonomers (other than ethylene) also typically compriseunits derived from propylene in an amount of at least about 60,preferably at least about 70 and more preferably at least about 80, wt %of the copolymer. The one or more unsaturated comonomers of thecopolymer comprise at least about 0.1, preferably at least about 1 andmore preferably at least about 3, weight percent, and the typicalmaximum amount of unsaturated comonomer does not exceed about 40, andpreferably it does not exceed about 30, wt % of the copolymer.

¹³C NMR

The copolymers of this invention are further characterized as havingsubstantially isotactic propylene sequences. “Substantially isotacticpropylene sequences” and similar terms mean that the sequences have anisotactic triad (mm) measured by ¹³C NMR of greater than about 0.85,preferably greater than about 0.90, more preferably greater than about0.92 and most preferably greater than about 0.93. Isotactic triads arewell known in the art and are described in, for example, U.S. Pat. No.5,504,172 and WO 00/01745 which refer to the isotactic sequence in termsof a triad unit in the copolymer molecular chain determined by ¹³C NMRspectra. NMR spectra are determined as follows.

¹³C NMR spectroscopy is one of a number of techniques known in the artof measuring comonomer incorporation into a polymer. An example of thistechnique is described for the determination of comonomer content forethylene/α-olefin copolymers in Randall (Journal of MacromolecularScience, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3),201–317 (1989)). The basic procedure for determining the comonomercontent of an olefin interpolymer involves obtaining the ¹³C NMRspectrum under conditions where the intensity of the peaks correspondingto the different carbons in the sample is directly proportional to thetotal number of contributing nuclei in the sample. Methods for ensuringthis proportionality are known in the art and involve allowance forsufficient time for relaxation after a pulse, the use ofgated-decoupling techniques, relaxation agents, and the like. Therelative intensity of a peak or group of peaks is obtained in practicefrom its computer-generated integral. After obtaining the spectrum andintegrating the peaks, those peaks associated with the comonomer areassigned. This assignment can be made by reference to known spectra orliterature, or by synthesis and analysis of model compounds, or by theuse of isotopically labeled comonomer. The mole % comonomer can bedetermined by the ratio of the integrals corresponding to the number ofmoles of comonomer to the integrals corresponding to the number of molesof all of the monomers in the interpolymer, as described in Randall, forexample.

The data is collected using a Varian UNITY Plus 400 MHz NMRspectrometer, corresponding to a ¹³C resonance frequency of 100.4 MHz.Acquisition parameters are selected to ensure quantitative ¹³C dataacquisition in the presence of the relaxation agent. The data isacquired using gated ¹H decoupling, 4000 transients per data file, a 7sec pulse repetition delay, spectral width of 24,200 Hz and a file sizeof 32K data points, with the probe head heated to 130° C. The sample isprepared by adding approximately 3 mL of a 50/50 mixture oftetrachloroethane-d2/orthodichlorobenzene that is 0.025M in chromiumacetylacetonate (relaxation agent) to 0.4 g sample in a 10 mm NMR tube.The headspace of the tube is purged of oxygen by displacement with purenitrogen. The sample is dissolved and homogenized by heating the tubeand its contents to 150° C. with periodic refluxing initiated by heatgun.

Following data collection, the chemical shifts are internally referencedto the mmmm pentad at 21.90 ppm.

For propylene/ethylene copolymers, the following procedure is used tocalculate the percent ethylene in the polymer. Integral regions aredetermined as follows:

TABLE D Integral Regions for Determining % Ethylene Region designationPpm A 44–49 B 36–39 C 32.8–34   P 31.0–30.8 Q Peak at 30.4 R Peak at 30F 28.0–29.7 G   26–28.3 H 24–26 I 19–23Region D is calculated as D=P−(G−Q)/2. Region E=R+Q+(G−Q)/2.

TABLE E Calculation of Region D PPP = (F + A − 0.5 D)/2 PPE = D EPE = CEEE = (E − 0.5 G)/2 PEE = G PEP = H Moles P = sum P centered triadsMoles E = sum E centered triads Moles P = (B + 2A)/2 Moles E = (E + G +0.5B + H)/2

C2 values are calculated as the average of the two methods above (triadsummation and algebraic) although the two do not usually vary.

The mole fraction of propylene insertions resulting in regio-errors iscalculated as one half of the sum of the two of methyls showing up at14.6 and 15.7 ppm divided by the total methyls at 14–22 ppm attributableto propylene. The mole percent of the regio-error peaks is the molefraction times 100.

Isotacticity at the triad level (mm) is determined from the integrals ofthe mm triad (22.70–21.28 ppm), the mr triad (21.28–20.67 ppm) and therr triad (20.67–19.74). The mm isotacticity is determined by dividingthe intensity of the mm triad by the sum of the mm, mr, and rr triads.For ethylene copolymers the mr region is corrected by subtracting37.5–39 ppm integral. For copolymers with other monomers that producepeaks in the regions of the mm, mr, and rr triads, the integrals forthese regions are similarly corrected by subtracting the intensity ofthe interfering peak using standard NMR techniques, once the peaks havebeen identified. This can be accomplished, for example, by analysis of aseries of copolymers of various levels of monomer incorporation, byliterature assignments, by isotopic labeling, or other means which areknown in the art.

The ¹³C NMR peaks corresponding to a regio-error at about 14.6 and about15.7 ppm are believed to be the result of stereoselective 2,1-insertionerrors of propylene units into the growing polymer chain. In a typicalpolymer of this invention, these peaks are of about equal intensity, andthey represent about 0.02 to about 7 mole percent of the propyleneinsertions into the homopolymer or copolymer chain. For some embodimentsof this invention, they represent about 0.005 to about 20 mole % or moreof the propylene insertions. In general, higher levels of regio-errorslead to a lowering of the melting point and the modulus of the polymer,while lower levels lead to a higher melting point and a higher modulusof the polymer.

It should be appreciated that the nature and level of comonomers otherthan propylene also control the melting point and modulus of thecopolymer. In any particular application, it may be desirable to haveeither a high or low melting point or a high or low modulus modulus. Thelevel of regio-errors can be controlled by several means, including thepolymerization temperature, the concentration of propylene and othermonomers in the process, the type of (co)monomers, and other factors.Various individual catalyst structures may inherently produce more orless regio-errors than other catalysts. For example, in Table A above,the propylene homopolymer prepared with Catalyst G has a higher level ofregio-errors and a lower melting point than the propylene homopolymerprepared with Catalyst H, which has a higher melting point. If a highermelting point (or higher modulus) polymer is desired, then it ispreferable to have fewer regio-errors than about 3 mole % of thepropylene insertions, more preferably less than about 1.5 mole % of thepropylene insertions, still more preferably less than about 1.0 mole %of the propylene insertions, and most preferably less than about 0.5mole % of the propylene insertions. If a lower melting point (ormodulus) polymer is desired, then it is preferable to have moreregio-errors than about 3 mole % of the propylene insertions, morepreferably more than about 5 mole % of the propylene insertions, stillmore preferably more than about 6 mole % of the propylene insertions,and most preferably more than about 10 mole % of the propyleneinsertions.

It should be appreciated by the skilled artisan that the mole % ofregio-errors for an inventive polymer which is a component of a blendrefers to the mole % of regio-errors of the particular inventive polymercomponent of the blend that is the particular inventive polymer, and notas a mole % of the overall blend.

The comparison of several ¹³C NMR sprectra further illustrates theunique regio-errors of the propylene polymers of this invention. FIGS. 6and 7 are the spectra of the propylene homopolymer products of Exampes 7and 8, respectively, each made with an activated nonmetallocene,metal-centered, heteroaryl ligand catalyst. The spectrum of each polymerreports a high degree of isotacticity and the unique regio-errors ofthese inventive polymers. FIG. 8 is the ¹³C NMR spectrum of thepropylene-ethylene copolymer of Example 2, made with the same catalystused to make the propylene homopolymer of Example 7, and it too reportsa high degree of isotacticity and the same regio-errors of the propylenehomopolymers of FIGS. 9 and 10. The presence of the ethylene comonomerdoes not preclude the occurrence of these unique regio-errors. The ¹³CNMR spectrum of FIG. 9 is that of the propylene-ethylene copolymerproduct of Comparative Example 1 which was prepared using a metallocenecatalyst. This spectrum does not report the regio-error (around 15 ppm)characteristic of the propylene polymers of this invention.

Melt Flow Rate (MFR)

The propylene copolymers of this invention typically have an MFR of atleast about 0.01, preferably at least about 0.05, more preferably atleast about 0.1 and most preferably at least about 0.2. The maximum MFRtypically does not exceed about 1,000, preferably it does not exceedabout 500, more preferably it does not exceed about 100, further morepreferably it does not exceed about 80 and most preferably it does notexceed about 50. MFR for polypropylene and copolymers of propylene andethylene and/or one or more C₄–C₂₀ α olefins is measured according toASTM D-1238, condition L (2.16 kg, 230 degrees C.).

Propylene Copolymers

The propylene copolymers of this invention of particular interestinclude propylene/ethylene, propylene/1-butene, propylene/1-hexene,propylene/4-methyl-1-pentene, propylene/1-octene,propylene/ethylene/1-butene, propylene/ethylene/ENB,propylene/ethylene/1-hexene, propylene/ethylene/1-octene,propylene/styrene, and propylene/ethylene/styrene.

Catalyst Definitions and Descriptions

The propylene copolymers of this invention are prepared by a processcomprising contacting under solution, slurry or gas phase polymerizationconditions propylene and at least one of ethylene and one or moreunsaturated monomers with a nonmetallocene, metal-centered, heteroarylligand catalyst. Propylene homopolymers are similarly prepared by aprocess comprising contacting under solution, slurry or gas phasepolymerization conditions propylene with a nonmetallocene,metal-centered, heteroaryl ligand catalyst. “Nonmetallocene” means thatthe metal of the catalyst is not attached to a substituted orunsubstituted cyclopentadienyl ring. Representative nonmetallocene,metal-centered, heteroarly ligand catalysts are described in U.S.Provisional Patent Application Nos. 60/246,781 filed Nov. 7, 2000 and60/301,666 filed Jun. 28, 2001.

As here used, “nonmetallocene, metal-centered, heteroaryl ligandcatalyst” means the catalyst derived from the ligand described informula I. As used in this phrase, “heteroaryl” includes substitutedheteroaryl.

As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, e.g., R¹, R², R³, R⁴, and R⁵ can beidentical or different (e.g. R¹, R², R³, R⁴, and R⁵ may all besubstituted alkyls or R¹ and R² may be a substituted alkyl and R³ may bean aryl, etc.). Use of the singular includes use of the plural and vicever-a (e.g., a hexane solvent, includes hexanes). A named R group willgenerally have the structure that is recognized in the art ascorresponding to R groups having that name. The terms “compound” and“complex” are generally used interchangeably in this specification, butthose of skill in the art may recognize certain compounds as complexesand vice versa. For the purposes of illustration, representative certaingroups are defined herein. These definitions are intended to supplementand illustrate, not preclude, the definitions known to those of skill inthe art.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 toabout 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including branched or unbranched,saturated or unsaturated species, such as alkyl groups, alkenyl groups,aryl groups, and the like. “Substituted hydrocarbyl” refers tohydrocarbyl substituted with one or more substituent groups, and theterms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” referto hydrocarbyl in which at least one carbon atom is replaced with aheteroatom.

The term “alkyl” is used herein to refer to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Suitable alkylradicals include, for example, methyl, ethyl, n-propyl, i-propyl,2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl), etc. In particular embodiments, alkyls have between 1and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20carbon atoms.

“Substituted alkyl” refers to an alkyl as just described in which one ormore hydrogen atom bound to any carbon of the alkyl is replaced byanother group such as a halogen, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,halogen, alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

The term “heteroalkyl” refers to an alkyl as described above in whichone or more hydrogen atoms to any carbon of the alkyl is replaced by aheteroatom selected from the group consisting of N, O, P, B, S, Si, Sb,Al, Sn, As, Se and Ge. This same list of heteroatoms is usefulthroughout this specification. The bond between the carbon atom and theheteroatom may be saturated or unsaturated. Thus, an alkyl substitutedwith a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, or seleno is within the scope of the term heteroalkyl. Suitableheteroalkyls include cyano, benzoyl, 2-pyridyl, 2-furyl and the like.

The term “cycloalkyl” is used herein to refer to a saturated orunsaturated cyclic non-aromatic hydrocarbon radical having a single ringor multiple condensed rings. Suitable cycloalkyl radicals include, forexample, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc. Inparticular embodiments, cycloalkyls have between 3 and 200 carbon atoms,between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.

“Substituted cycloalkyl” refers to cycloalkyl as just describedincluding in which one or more hydrogen atom to any carbon of thecycloalkyl is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substituted cycloalkylradicals include, for example, 4-dimethylaminocyclohexyl,4,5-dibromocyclohept-4-enyl, and the like.

The term “heterocycloalkyl” is used herein to refer to a cycloalkylradical as described, but in which one or more or all carbon atoms ofthe saturated or unsaturated cyclic radical are replaced by a heteroatomsuch as nitrogen, phosphorous, oxygen, sulfur, silicon, germanium,selenium, or boron. Suitable heterocycloalkyls include, for example,piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl,piperidinyl, pyrrolidinyl, oxazolinyl and the like.

“Substituted heterocycloalkyl” refers to heterocycloalkyl as justdescribed including in which one or more hydrogen atom to any atom ofthe heterocycloalkyl is replaced by another group such as a halogen,alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substitutedheterocycloalkyl radicals include, for example, N-methylpiperazinyl,3-dimethylaminomorpholinyl and the like.

The term “aryl” is used herein to refer to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. In particularembodiments, aryls have between 1 and 200 carbon atoms, between 1 and 50carbon atoms or between 1 and 20 carbon atoms.

“Substituted aryl” refers to aryl as just described in which one or morehydrogen atom bound to any carbon is replaced by one or more functionalgroups such as alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen,alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy, amino, thio,nitro, and both saturated and unsaturated cyclic hydrocarbons which arefused to the aromatic ring(s), linked covalently or linked to a commongroup such as a methylene or ethylene moiety. The common linking groupmay also be a carbonyl as in benzophenone or oxygen as in diphenyletheror nitrogen in diphenylamine.

The term “heteroaryl” as used herein refers to aromatic or unsaturatedrings in which one or more carbon atoms of the aromatic ring(s) arereplaced by a heteroatom(s) such as nitrogen, oxygen, boron, selenium,phosphorus, silicon or sulfur. Heteroaryl refers to structures that maybe a single aromatic ring, multiple aromatic ring(s), or one or morearomatic rings coupled to one or more non-aromatic ring(s). Instructures having multiple rings, the rings can be fused together,linked covalently, or linked to a common group such as a methylene orethylene moiety. The common linking group may also be a carbonyl as inphenyl pyridyl ketone. As used herein, rings such as thiophene,pyridine, isoxazole, pyrazole, pyrrole, furan, etc. or benzo-fusedanalogues of these rings are defined by the term “heteroaryl.”

“Substituted heteroaryl” refers to heteroaryl as just describedincluding in which one or more hydrogen atoms bound to any atom of theheteroaryl moiety is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio,seleno and combinations thereof. Suitable substituted heteroarylradicals include, for example, 4-N,N-dimethylaminopyridine.

The term “alkoxy” is used herein to refer to the —OZ¹ radical, where Z¹is selected from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substitutedheterocycloalkyl, silyl groups and combinations thereof as describedherein. Suitable alkoxy radicals include, for example, methoxy, ethoxy,benzyloxy, t-butoxy, etc. A related term is “aryloxy” where Z¹ isselected from the group consisting of aryl, substituted aryl,heteroaryl, substituted heteroaryl, and combinations thereof. Examplesof suitable aryloxy radicals include phenoxy, substituted phenoxy,2-pyridinoxy, 8-quinalinoxy and the like.

As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical, whereeach of Z¹, Z², and Z³ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinationsthereof.

As used herein the term “boryl” refers to the —BZ¹Z² group, where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.

As used herein, the term “phosphino” refers to the group—PZ¹Z², whereeach of Z¹ and Z² is independently selected from the group consisting ofhydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

As used herein, the term “phosphine” refers to the group: PZ¹Z²Z³, whereeach of Z¹, Z³ and Z² is independently selected from the groupconsisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

The term “amino” is used herein to refer to the group —NZ¹Z², where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl andcombinations thereof.

The term “amine” is used herein to refer to the group: NZ¹Z²Z³, whereeach of Z¹, Z² and Z² is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl (including pyridines), substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “thio” is used herein to refer to the group —SZ¹, where Z¹ isselected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “seleno” is used herein to refer to the group —SeZ¹, where Z¹is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “saturated” refers to lack of double and triple bonds betweenatoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, andthe like.

The term “unsaturated” refers to the presence one or more double and/ortriple bonds between atoms of a radical group such as vinyl, acetylide,oxazolinyl, cyclohexenyl, acetyl and the like.

Ligands

Suitable ligands useful in the catalysts used in the practice of thisinvention can be characterized broadly as monoanionic ligands having anamine and a heteroaryl or substituted heteroaryl group. The ligands ofthe catalysts used in the practice of this invention are referred to,for the purposes of this invention, as nonmetallocene ligands, and maybe characterized by the following general formula:

wherein R¹ is very generally selected from the group consisting ofalkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl and combinations thereof. In many embodiments, R¹ is a ringhaving from 4–8 atoms in the ring generally selected from the groupconsisting of substituted cycloalkyl, substituted heterocycloalkyl,substituted aryl and substituted heteroaryl, such that R¹ may becharacterized by the general formula:

where Q¹ and Q⁵ are substituents on the ring ortho to atom E, with Ebeing selected from the group consisting of carbon and nitrogen and withat least one of Q¹ or Q⁵ being bulky (defined as having at least 2atoms). Q¹ and Q⁵ are independently selected from the group consistingof alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl,substituted aryl and silyl, but provided that Q¹ and Q⁵ are not bothmethyl. Q″_(q) represents additional possible substituents on the ring,with q being 1, 2, 3, 4 or 5 and Q″ being selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof.T is a bridging group selected group consisting of —CR²R³— and —SiR²R³—with R² and R³ being independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof. J″ is generallyselected from the group consisting of heteroaryl and substitutedheteroaryl, with particular embodiments for particular reactions beingdescribed herein.

In a more specific embodiment, suitable nonmetallocene ligands useful inthis invention may be characterized by the following general formula:

wherein R¹ and T are as defined above and each of R⁴, R⁵, R⁶ and R⁷ isindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof. Optionally, any combination of R¹, R², R³ andR⁴ may be joined together in a ring structure.

In certain more specific embodiments, the ligands in this invention maybe characterized by the following general formula:

wherein Q¹, Q⁵, R², R³, R⁴, R⁵, R⁶ and R⁷ are as defined above. Q², Q³and Q⁴ are independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, nitro, and combinations thereof.

In other more specific embodiments, the ligands of this invention andsuitable herein may be characterized by the following general formula:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are as defined above. In thisembodiment the R⁷ substituent has been replaced with an aryl orsubstituted aryl group, with R¹⁰, R¹¹, R¹² and R¹³ being independentlyselected from the group consisting of hydrogen, halo, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3–50 non-hydrogen atoms.R¹⁴ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof.

In still more specific embodiments, the ligands in this invention may becharacterized by the general formula:

wherein R²–R⁶, R¹⁰–R¹⁴ and Q¹–Q⁵ are all as defined above.

In certain embodiments, R² is preferably hydrogen. Also preferably, eachof R⁴ and R⁵ is hydrogen and R⁶ is either hydrogen or is joined to R⁷ toform a fused ring system. Also preferred is where R³ is selected fromthe group consisting of benzyl, phenyl, 2-biphenyl, t-butyl,2-dimethylaminophenyl (2-(NMe₂)-C₆H₄-), 2-methoxyphenyl (2-MeO—C₆H₄—),anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl,9-phenanthrenyl. Also preferred is where R¹ is selected from the groupconsisting of mesityl, 4-isopropylphenyl (4-Pr^(i)—C₆H₄—), napthyl,3,5-(CF₃)₂—C₆H₃—, 2-Me-napthyl, 2,6-(Pr^(i))₂—C₆H₃—, 2-biphenyl,2-Me-4-MeO—C₆H₃—; 2-Bu^(t)-C₆H₄—, 2,5-(Bu^(t))₂-C₆H₃—,2-Pr^(i)-6-Me-C₆H₃—; 2-Bu^(t)-6-Me-C₆H₃—, 2,6-Et₂-C₆H₃—,2-sec-butyl-6-Et-C₆H₃— Also preferred is where R⁷ is selected from thegroup consisting of hydrogen, phenyl, napthyl, methyl, anthracenyl,9-phenanthrenyl, mesityl, 3,5-(CF₃)₂—C₆H₃—, 2-CF₃—C₆H₄—, 4-CF₃—C₆H₄—,3,5-F₂—C₆H₃—, 4-F—C₆H₄—, 2,4-F₂—C₆H₃—, 4-(NMe₂)-C₆H₄—, 3-MeO—C₆H₄—,4-MeO—C₆H₄—, 3,5-Me₂-C₆H₃—, o-tolyl, 2,6-F₂—C₆H₃— or where R⁷ is joinedtogether with R⁶ to form a fused ring system, e.g., quinoline.

Also optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joined to forma fused ring system having from 3–50 non-hydrogen atoms in addition tothe pyridine ring, e.g. generating a quinoline group. In theseembodiments, R³ is selected from the group consisting of aryl,substituted aryl, heteroaryl, substituted heteroaryl, primary andsecondary alkyl groups, and —PY₂ where Y is selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.

Optionally within above formulas IV and V, R⁶ and R¹⁰ may be joined toform a ring system having from 5–50 non-hydrogen atoms. For example, ifR⁶ and R¹⁰ together form a methylene, the ring will have 5 atoms in thebackbone of the ring, which may or may not be substituted with otheratoms. Also for example, if R⁶ and R¹⁰ together form an ethylene, thering will have 6 atoms in the backbone of the ring, which may or may notbe substituted with other atoms. Substituents from the ring can beselected from the group consisting of halo, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof.

In certain embodiments, the ligands are novel compounds and those ofskill in the art will be able to identify such compounds from the above.One example of the novel ligand compounds, includes those compoundsgenerally characterized by formula (III), above where R² is selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, aryl, and substituted aryl; and R³is a phosphino characterized by the formula —PZ¹Z², where each of Z¹ andZ² is independently selected from the group consisting of hydrogen,substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, silyl, alkoxy,aryloxy, amino and combinations thereof. Particularly preferredembodiments of these compounds include those where Z¹ and Z² are eachindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, heterocycloalkyl, aryl, and substituted aryl; andmore specifically phenyl; where Q¹, Q³, and Q⁵ are each selected fromthe group consisting of alkyl and substituted alkyl and each of Q² andQ⁴ is hydrogen; and where R⁴, R⁵, R⁶ and R⁷ are each hydrogen.

The ligands of the catalysts of this invention may be prepared usingknown procedures. See, for example, Advanced Organic Chemistry, March,Wiley, New York 1992 (4^(th) Ed.). Specifically, the ligands of theinvention may be prepared using the two step procedure outlined inScheme 1.

In Scheme 1, the * represents a chiral center when R² and R³ are notidentical; also, the R groups have the same definitions as above.Generally, R³M² is a nucleophile such as an alkylating or arylating orhydrogenating reagent and M² is a metal such as a main group metal, or ametalloid such as boron. The alkylating, arylating or hydrogenatingreagent may be a Grignard, alkyl, aryl-lithium or borohydride reagent.Scheme 1, step 2 first employs the use of complexing reagent.Preferably, as in the case of Scheme 1, magnesium bromide is used as thecomplexing reagent. The role of the complexing reagent is to direct thenucleophile, R³M², selectively to the imine carbon. Where the presenceof functional groups impede this synthetic approach, alternativesynthetic strategies may be employed. For instance, ligands whereR³=phosphino can be prepared in accordance with the teachings of U.S.Pat. Nos. 6,034,240 and 6,043,363. In addition, tetra-alkylhafniumcompounds or tetra-substituted alkylhafnium compounds ortetra-arylhafnium compounds or tetra-substituted arylhafnium compoundsmay be employed in step 2, in accordance with the teachings of U.S. Pat.No. 6,103,657. Scheme 2 further describes a synthesis process:

In scheme 2, h=1 or 2 and the bromine ions may or may not be bound tothe magnesium. The effect of the complexation is to guide the subsequentnucleophilic attack by R³ M² to the imine carbon. Thus complexation maylead to a more selective reaction that may increase the yield of thedesired ancillary ligands. Using this technique, selectivity isgenerally greater than about 50%, more preferably greater than about 70%and even more preferably greater than about 80%. Complexation may beparticularly useful for the preparation of arrays of ancillary ligandsof the type disclosed in the invention, where R³ is a variable in thepreparation of the ancillary ligand array. As shown in Scheme 2 by the*, where R² and R³ are different, this approach also leads to theformation of a chiral center on the ancillary ligands of the invention.Under some circumstances R³M² may be successfully added to the imine inthe absence the complexing reagent. Ancillary ligands that possesschirality may be important in certain olefin polymerization reactions,particularly those that lead to a stereospecific polymer, see“Stereospecific Olefin Polymerization with Chiral MetalloceneCatalysts”, Brintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, Vol.34, pp. 1143–1170, and the references therein; Bercaw et al., J. Am.Chem. Soc., 1999, Vol. 121, 564–573; and Bercaw et al., J. Am. Chem.Soc., 1996, Vol. 118, 11988–11989.

In the practice of high throughput methods or combinatorial materialsscience, introduction of diversity may be important in designinglibraries or arrays. The synthetic schemes discussed herein will allowthose of skill in the art to introduce diversity on the ligands, whichmay assist in optimizing the selection of a particular ligand for aparticular polymerization reaction. Step 1 (see Scheme 1) may beconducted with, for example, any combination of pyridines and anilinesshown herein.

Compositions

Once the desired ligand is formed, it may be combined with a metal atom,ion, compound or other metal precursor compound. In some applications,the ligands of this invention will be combined with a metal compound orprecursor and the product of such combination is not determined, if aproduct forms. For example, the ligand may be added to a reaction vesselat the same time as the metal or metal precursor compound along with thereactants, activators, scavengers, etc. Additionally, the ligand can bemodified prior to addition to or after the addition of the metalprecursor, e.g. through a deprotonation reaction or some othermodification.

For formulas I, II, III, IV and V, the metal precursor compounds may becharacterized by the general formula Hf(L)_(n) where L is independentlyselected from the group consisting of halide (F, Cl, Br, I), alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, and combinations thereof. nis 1, 2, 3, 4, 5, or 6. The hafnium precursors may be monomeric, dimericor higher orders thereof. It is well known that hafnium metal typicallycontains some amount of impurity of zirconium. Thus, this invention usesas pure hafnium as is commercially reasonable. Specific examples ofsuitable hafnium precursors include, but are not limited to HfCl₄,Hf(CH₂Ph)₄, Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂. Lewis base adducts of theseexamples are also suitable as hafnium precursors, for example, ethers,amines, thioethers, phosphines and the like are suitable as Lewis bases.

For formulas IV and V, the metal precursor compounds may becharacterized by the general formula M(L)_(n) where M is hafnium orzirconium and each L is independently selected from the group consistingof halide (F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, and combinations thereof. n is 4, typically. It iswell known that hafnium metal typically contains some amount of impurityof zirconium. Thus, this invention uses as pure hafnium or zirconium asis commercially reasonable. Specific examples of suitable hafnium andzirconium precursors include, but are not limited to HfCl₄, Hf(CH₂Ph)₄,Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂; ZrCl₄, Zr(CH₂Ph)₄,Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)₄, Zr(CH₂Ph)₃Cl, Zr(CH₂CMe₃)₃Cl,Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂, Zr(CH₂CMe₃)₂Cl₂, Zr(CH₂SiMe₃)₂Cl₂,Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMe₂)₂Cl₂, Zr(NEt₂)₂Cl₂, and Zr(N(SiMe₃)₂)₂Cl₂.Lewis base adducts of these examples are also suitable as hafniumprecursors, for example, ethers, amines, thioethers, phosphines and thelike are suitable as Lewis bases.

The ligand to metal precursor compound ratio is typically in the rangeof about 0.01:1 to about 100: 1, more preferably in the range of about0.1:1 to about 10:1.

Metal-Ligand Complexes

This invention, in part, relates to the use of nonmetallocenemetal-ligand complexes. Generally, the ligand is mixed with a suitablemetal precursor compound prior to or simultaneously with allowing themixture to be contacted with the reactants (e.g., monomers). When theligand is mixed with the metal precursor compound, a metal-ligandcomplex may be formed, which may be a catalyst or may need to beactivated to be a catalyst. The metal-ligand complexes discussed hereinare referred to as 2,1 complexes or 3,2 complexes, with the first numberrepresenting the number of coordinating atoms and second numberrepresenting the charge occupied on the metal. The 2,1-complexestherefore have two coordinating atoms and a single anionic charge. Otherembodiments of this invention are those complexes that have a general3,2 coordination scheme to a metal center, with 3,2 referring to aligand that occupies three coordination sites on the metal and two ofthose sites being anionic and the remaining site being a neutral Lewisbase type coordination.

Looking first at the 2,1-nonmetallocene metal-ligand complexes, themetal-ligand complexes may be characterized by the following generalformula:

wherein T, J″, R¹, L and n are as defined previously; and x is 1 or 2.The J″ heteroaryl may or may not datively bond, but is drawn as bonding.More specifically, the nonmetallocene-ligand complexes may becharacterized by the formula:

wherein R¹, T, R⁴, R⁵, R⁶, R⁷, L and n are as defined previously; and xis 1 or 2. In one preferred embodiment x=1 and n=3. Additionally, Lewisbase adducts of these metal-ligand complexes are also within the scopeof the invention, for example, ethers, amines, thioethers, phosphinesand the like are suitable as Lewis bases.

More specifically, the nonmetallocene metal-ligand complexes of thisinvention may be characterized by the general formula:

wherein the variables are generally defined above. Thus, e.g., Q², Q³,Q⁴, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof;optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joined to form afused ring system having from 3–50 non-hydrogen atoms in addition to thepyridine ring, e.g. generating a quinoline group; also, optionally, anycombination of R², R³ and R⁴ may be joined together in a ring structure;Q¹ and Q⁵ are selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl,provided that Q¹ and Q⁵ are not both methyl; and each L is independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkylheterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates and combinations thereof; n is 1, 2, 3, 4, 5, or 6;and x=1 or 2.

In other embodiments, the 2,1 metal-ligand complexes can becharacterized by the general formula:

wherein the variables are generally defined above.

In still other embodiments, the 2,1 metal-ligand complexes of thisinvention can be characterized by the general formula:

wherein the variables are generally defined above.

The more specific embodiments of the nonmetallocene metal-ligandcomplexes of formulas VI, VII, VIII, IX and X are explained above withregard to the specifics described for the ligands and metal precursors.Specific examples of 2,1 metal-ligand complexes include, but are notlimited to:

where L, n and x are defined as above (e.g., x=1 or 2) and Ph=phenyl. Inpreferred embodiments, x=1 and n=3. Furthermore in preferredembodiments, L is selected from the group consisting of alkyl,substituted alkyl, aryl, substituted aryl or amino.

Turning to the 3,2 metal-ligand nonmetallocene complexes used in thepractice of this invention, the metal-ligand complexes may becharacterized by the general formula:

where M is zirconium or hafnium;

R¹ and T are defined above;

J′″ being selected from the group of substituted heteroaryls with 2atoms bonded to the metal M, at least one of those 2 atoms being aheteroatom, and with one atom of J′″ is bonded to M via a dative bond,the other through a covalent bond; and

L¹ and L² are independently selected from the group consisting ofhalide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine,hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio,1,3-dionates, oxalates, carbonates, nitrates, sulphates, andcombinations thereof.

More specifically, the 3,2 metal-ligand nonmetallocene complexes of thisinvention may be characterized by the general formula:

where M is zirconium or hafnium;

T, R¹, R⁴, R⁵, R⁶, L¹ and L² are defined above; and

E″ is either carbon or nitrogen and is part of an cyclic aryl,substituted aryl, heteroaryl, or substituted heteroaryl group.

Even more specifically, the 3,2 metal-ligand nonmetallocene complexesused in the practice of this invention may be characterized by thegeneral formula:

where M is zirconium or hafnium; and

T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, L¹ and L² are defined above.

Still even more specifically, the 3,2 metal-ligand nonmetallocenecomplexes of this invention may be characterized by the general formula:

where M is zirconium or hafnium; and

T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, Q¹, Q², Q³, Q⁴, Q⁵, L¹ and L² aredefined above.

The more specific embodiments of the metal-ligand complexes of formulasXI, XII, XIII and XIV are explained above with regard to the specificsdescribed for the ligands and metal precursors.

In the above formulas, R¹⁰, R¹¹, R¹² and R¹³ are independently selectedfrom the group consisting of hydrogen, halo, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof, optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3–50 non-hydrogen atoms.

In addition, Lewis base adducts of the metal-ligand complexes in theabove formulas are also suitable, for example, ethers, amines,thioethers, phosphines and the like are suitable as Lewis bases.

The metal-ligand complexes can be formed by techniques known to those ofskill in the art. In some embodiments, R¹⁴ is hydrogen and themetal-ligand complexes are formed by a metallation reaction (in situ ornot) as shown below in scheme 3:

In scheme 3, R¹⁴ is hydrogen (but see above for the full definition ofR¹⁴ in other embodiments of this invention). The metallation reaction toconvert the 2,1-complex on the left to the 3,2 complex on the right canoccur via a number of mechanisms, likely depending on the substituentschosen for L¹, L² and L³ and the other substituents such as Q¹–Q⁵,R²–R⁶, R¹⁰ to R¹³. In one embodiment, when L¹, L² and L³ are eachN(CH₃)₂, the reaction can proceed by heating the 2,1 complex to atemperature above about 100° C. In this embodiment, it is believed thatL¹ and L² remain N(CH₃)₂ in the 3,2 complex. In another embodiment whereL¹, L² and L³ are each N(CH₃)₂, the reaction can proceed by adding agroup 13 reagent (as described below) to the 2,1 complex at a suitabletemperature (such as room temperature). Preferably the group 13 reagentfor this purpose is di-isobutyl aluminum hydride, tri-isobutyl aluminumor trimethyl aluminum. In this embodiment, L¹ and L² are typicallyconverted to the ligand (e.g., alkyl or hydride) stemming from the group13 reagent (e.g., from trimethyl aluminum, L¹ and L² are each CH₃ in the3,2 complex). The 2,1 complex in scheme 3 is formed by the methodsdiscussed above.

In an alternative embodiment possibly outside the scope of scheme 3, forisotactic polypropylene production, it is currently preferred that R¹⁴is either hydrogen or methyl.

Specific examples of 3,2 complexes of this invention include:

Various references disclose metal complexes that may appear to besimilar; see for example, U.S. Pat. Nos. 6,103,657 and 5,637,660.However, certain embodiments of the invention herein provideunexpectedly improved polymerization performance (e.g., higher activityand/or higher polymerization temperatures and/or higher comonomerincorporation and/or crystalline polymers resulting from a high degreeof stereoselectivity during polymerization) relative to the embodimentsdisclosed in those references. In particular, as shown in certain of theexamples herein, the activity of the hafnium metal catalysts is farsuperior to that of the zirconium catalysts.

The ligands, complexes or catalysts may be supported on an organic orinorganic support. Suitable supports include silicas, aluminas, clays,zeolites, magnesium chloride, polyethyleneglycols, polystyrenes,polyesters, polyamides, peptides and the like. Polymeric supports may becross-linked or not. Similarly, the ligands, complexes or catalysts maybe supported on similar supports known to those of skill in the art. Inaddition, the catalysts of this invention may be combined with othercatalysts in a single reactor and/or employed in a series of reactors(parallel or serial) in order to form blends of polymer products.Supported catalysts typically produce copolymers of this invention withan MWD larger than those produce from unsupported catalysts., althoughthese MWDs are typically less about 6, preferably less than about 5 andmore preferably less than about 4. While not wanting to be bound by anyparticular theory of operation, the unsupported catalysts typicallyproduce P/E* polymers with a narrow MWD which suggests that thenonmetallocene, metal-centered, heteroaryl ligand catalysts used in thepractice of this invention are “single-site” catalysts.

The metal complexes used in this invention are rendered catalyticallyactive by combination with an activating cocatalyst or by use of anactivating technique. Suitable activating cocatalysts for use hereininclude neutral Lewis acids such as alumoxane (modified and unmodified),C₁₋₃₀ hydrocarbyl substituted Group 13 compounds, especiallytri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds andhalogenated (including perhalogenated) derivatives thereof, having from1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group,more especially perfluorinated tri(aryl)boron compounds, and mostespecially tris(pentafluorophenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium salts of compatible,noncoordinating anions; bulk electrolysis (explained in more detailhereinafter); and combinations of the foregoing activating cocatalystsand techniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes in the following references: U.S. Pat. Nos. 5,153,157 and5,064,802, EP-A-277,003, EP-A-468,651 (equivalent to U.S. Ser. No.07/547,718), U.S. Pat. Nos. 5,721,185 and 5,350,723.

The alumoxane used as an activating cocatalyst in this invention is ofthe formula (R⁴ _(X)(CH₃)_(y)AlO)_(n), in which R⁴ is a linear, branchedor cyclic C₁ to C₆ hydrocarbyl, x is from 0 to about 1, y is from about1 to 0, and n is an integer from about 3 to about 25, inclusive. Thepreferred alumoxane components, referred to as modifiedmethylaluminoxanes, are those wherein R⁴ is a linear, branched or cyclicC₃ to C₉ hydrocarbyl, x is from about 0.15 to about 0.50, y is fromabout 0.85 to about 0.5 and n is an integer between 4 and 20, inclusive;still more preferably, R⁴ is isobutyl, tertiary butyl or n-octyl, x isfrom about 0.2 to about 0.4, y is from about 0.8 to about 0.6 and n isan integer between 4 and 15, inclusive. Mixtures of the above alumoxanesmay also be employed in the practice of the invention.

Most preferably, the alumoxane is of the formula (R⁴_(X)(CH₃)_(y)AlO)_(n), wherein R⁴ is isobutyl or tertiary butyl, x isabout 0.25, y is about 0.75 and n is from about 6 to about 8.

Particularly preferred alumoxanes are so-called modified alumoxanes,preferably modified methylalumoxanes (MMAO), that are completely solublein alkane solvents, for example heptane, and may include very little, ifany, trialkylaluminum. A technique for preparing such modifiedalumoxanes is disclosed in U.S. Pat. No. 5,041,584 (which isincorporated by reference). Alumoxanes useful as an activatingcocatalyst in this invention may also be made as disclosed in U.S. Pat.Nos. 4,542,199; 4,544,762; 4,960,878; 5,015,749; 5,041,583 and5,041,585. Various alumoxanes can be obtained from commercial sources,for example, Akzo-Nobel Corporation, and include MMAO-3A, MMAO-12, andPMAO-IP.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to10 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, and combinations of neutral Lewis acids,especially tris(pentafluorophenyl)borane, with nonpolymeric, compatiblenoncoordinating ion-forming compounds are also useful activatingcocatalysts.

Suitable ion forming compounds useful as cocatalysts in one embodimentof the present invention comprise a cation which is a Bronsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” means an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derivedtherefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

In one embodiment of this invention, the activating cocatalysts may berepresented by the following general formula:[L*−H]⁺ _(d)[A^(d−)]wherein:

L* is a neutral Lewis base;

[L*−H]⁺ is a Bronsted acid;

A^(d−) is a noncoordinating, compatible anion having a charge of d⁻, and

d is an integer from 1 to 3.

More preferably A^(d−) corresponds to the formula: [M′^(k+)Q_(n)′]^(d−)wherein:

k is an integer from 1 to 3;

n′ is an integer from 2 to 6;

n′−k=d;

M′ is an element selected from Group 13 of the Periodic Table of theElements; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, hydrocarbyl, hydrocarbyloxy, halosubstituted-hydrocarbyl,halosubstituted hydrocarbyloxy, and halo substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, i.e., the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:[L*−H]⁺[BQ₄]⁻wherein:

[L*−H]⁺ is as previously defined;

B is boron in an oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy- or fluorinated silylhydrocarbyl-group of upto 20 nonhydrogen atoms, with the proviso that in not more than oneoccasion is Q hydrocarbyl. Most preferably, Q is each occurrence afluorinated aryl group, especially, a pentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the catalysts ofthis invention are tri-substituted ammonium salts such as:

-   triethylammonium tetraphenylborate,-   N,N-dimethylanilinium tetraphenylborate,-   tripropylammonium tetrakis(pentafluorophenyl) borate,-   N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,-   triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,-   N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate, and-   N,N-dimethyl-2,4,6-trimethylanilinium    tetrakis(2,3,4,6-tetrafluorophenyl) borate;-   dialkyl ammonium salts such as:-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and-   dicyclohexylammonium tetrakis(pentafluorophenyl) borate;-   tri-substituted phosphonium salts such as:-   triphenylphosphonium tetrakis(pentafluorophenyl) borate,-   tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and-   tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)    borate;-   di-substituted oxonium salts such as:-   diphenyloxonium tetrakis(pentafluorophenyl) borate,-   di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and-   di(2,6-dimethylphenyl)oxonium tetrakis(pentafluorophenyl) borate;-   di-substituted sulfonium salts such as:-   diphenylsulfonium tetrakis(pentafluorophenyl) borate,-   di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and-   di(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl) borate.

Preferred [L*−H]⁺ cations are N,N-dimethylanilinium andtributylammonium.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Ox^(e+))_(d)(A^(d−))_(e)wherein:

Ox^(e+) is a cationic oxidizing agent having a charge of e⁺;

e is an integer from 1 to 3; and

A^(d−) and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:{circle around (C)}⁺A⁻wherein:

{circle around (C)}⁺ is a C₁₋₂₀ carbenium ion; and

A⁻ is as previously defined.

A preferred carbenium ion is the trityl cation, i.e.,triphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:R₃Si(X′)_(q) ⁺A⁻wherein:

R is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakis(pentafluorophenyl)borate,triethylsilylium(tetrakispentafluoro)phenylborate and ether substitutedadducts thereof. Silylium salts have been previously genericallydisclosed in J. Chem Soc. Chem. Comm., 1993, 383–384, as well asLambert, J. B., et al., Organometallics, 1994, 13, 2430–2443.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

The technique of bulk electrolysis involves the electrochemicaloxidation of the metal complex under electrolysis conditions in thepresence of a supporting electrolyte comprising a noncoordinating, inertanion. In the technique, solvents, supporting electrolytes andelectrolytic potentials for the electrolysis are used such thatelectrolysis byproducts that would render the metal complexcatalytically inactive are not substantially formed during the reaction.More particularly, suitable solvents are materials that are: liquidsunder the conditions of the electrolysis (generally temperatures from 0to 100 C), capable of dissolving the supporting electrolyte, and inert.“Inert solvents” are those that are not reduced or oxidized under thereaction conditions employed for the electrolysis. It is generallypossible in view of the desired electrolysis reaction to choose asolvent and a supporting electrolyte that are unaffected by theelectrical potential used for the desired electrolysis. Preferredsolvents include difluorobenzene (all isomers), dimethoxyethane (DME),and mixtures thereof.

The electrolysis may be conducted in a standard electrolytic cellcontaining an anode and cathode (also referred to as the workingelectrode and counter electrode respectively). Suitable materials ofconstruction for the cell are glass, plastic, ceramic and glass coatedmetal. The electrodes are prepared from inert conductive materials, bywhich are meant conductive materials that are unaffected by the reactionmixture or reaction conditions. Platinum or palladium are preferredinert conductive materials. Normally an ion permeable membrane such as afine glass frit separates the cell into separate compartments, theworking electrode compartment and counter electrode compartment. Theworking electrode is immersed in a reaction medium comprising the metalcomplex to be activated, solvent, supporting electrolyte, and any othermaterials desired for moderating the electrolysis or stabilizing theresulting complex. The counter electrode is immersed in a mixture of thesolvent and supporting electrolyte. The desired voltage may bedetermined by theoretical calculations or experimentally by sweeping thecell using a reference electrode such as a silver electrode immersed inthe cell electrolyte. The background cell current, the current draw inthe absence of the desired electrolysis, is also determined. Theelectrolysis is completed when the current drops from the desired levelto the background level. In this manner, complete conversion of theinitial metal complex can be easily detected.

Suitable supporting electrolytes are salts comprising a cation and acompatible, noncoordinating anion, A⁻. Preferred supporting electrolytesare salts corresponding to the formula:G⁺A⁻wherein:

G⁺ is a cation which is nonreactive towards the starting and resultingcomplex, and

A⁻ is as previously defined.

Examples of cations, G⁺, include tetrahydrocarbyl substituted ammoniumor phosphonium cations having up to 40 nonhydrogen atoms. Preferredcations are the tetra-n-butylammonium- and tetraethylammonium-cations.

During activation of the complexes of the present invention by bulkelectrolysis the cation of the supporting electrolyte passes to thecounter electrode and A⁻ migrates to the working electrode to become theanion of the resulting oxidized product. Either the solvent or thecation of the supporting electrolyte is reduced at the counter electrodein equal molar quantity with the amount of oxidized metal complex formedat the working electrode. Preferred supporting electrolytes aretetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates havingfrom 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group,especially tetra-n-butylammonium tetrakis(pentafluorophenyl) borate.

A further discovered electrochemical technique for generation ofactivating cocatalysts is the electrolysis of a disilane compound in thepresence of a source of a noncoordinating compatible anion. Thistechnique is more fully disclosed and claimed in U.S. Pat. No.5,625,087.

The foregoing activating techniques and ion forming cocatalysts are alsopreferably used in combination with a tri(hydrocarbyl)aluminum ortri(hydrocarbyl)borane compound having from 1 to 4 carbons in eachhydrocarbyl group.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:100 to 1:1. In one embodiment of the invention the cocatalyst canbe used in combination with a tri(hydrocarbyl)aluminum compound havingfrom 1 to 10 carbons in each hydrocarbyl group. Mixtures of activatingcocatalysts may also be employed. It is possible to employ thesealuminum compounds for their beneficial ability to scavenge impuritiessuch as oxygen, water, and aldehydes from the polymerization mixture.Preferred aluminum compounds include trialkyl aluminum compounds havingfrom 1 to 6 carbons in each alkyl group, especially those wherein thealkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,pentyl, neopentyl or isopentyl. The molar ratio of metal complex toaluminum compound is preferably from 1:10,000 to 100:1, more preferablyfrom 1:1000 to 10:1, most preferably from 1:500 to 1:1. A most preferredborane activating cocatalyst comprises a strong Lewis acid, especiallytris(pentafluorophenyl)borane.

In some embodiments disclosed herein, two or more different catalysts,including the use of mixed catalysts can be employed. In addition to anonmetallocene, metal-centered, heteroaryl ligand catalyst, when aplurality of catalysts are used, any catalyst which is capable ofcopolymerizing one or more olefin monomers to make an interpolymer orhomopolymer may be used in embodiments of the invention in conjunctionwith a nonmetallocene, metal-centered, heteroaryl ligand catalyst. Forcertain embodiments, additional selection criteria, such as molecularweight capability and/or comonomer incorporation capability, preferablyshould be satisfied. Two or more nonmetallocene, metal-centered,heteroaryl ligand catalysts having different substituents can be used inthe practice of certain of the embodiments disclosed herein. Suitablecatalysts which may be used in conjunction with the nonmetallocene,metal-centered, heteroaryl ligand catalysts disclosed herein include,but are not limited to, metallocene catalysts and constrained geometrycatalysts, multi-site catalysts (Ziegler-Natta catalysts), andvariations therefrom. They include any known and presently unknowncatalysts for olefin polymerization. It should be understood that theterm “catalyst” as used herein refers to a metal-containing compoundwhich is used, along with an activating cocatalyst, to form a catalystsystem. The catalyst, as used herein, is usually catalytically inactivein the absence of a cocatalyst or other activating technique. However,not all suitable catalysts are catalytically inactive without acocatalyst.

One suitable class of catalysts is the constrained geometry catalystsdisclosed in U.S. Pat. Nos. 5,064,802, 5,132,380, 5,703,187, 6,034,021,EP 0 468 651, EP 0 514 828, WO 93/19104, and WO 95/00526, all of whichare incorporated by references herein in their entirety. Anothersuitable class of catalysts is the metallocene catalysts disclosed inU.S. Pat. Nos. 5,044,438, 5,057,475, 5,096,867, and 5,324,800, all ofwhich are incorporated by reference herein in their entirety. It isnoted that constrained geometry catalysts may be considered asmetallocene catalysts, and both are sometimes referred to in the art assingle-site catalysts.

Another suitable class of catalysts is substituted indenyl containingmetal complexes as disclosed in U.S. Pat. Nos. 5,965,756 and 6,015,868.Other catalysts are disclosed in U.S. Pat. Nos. 6,268,444 and 6,515,155and in U.S. Ser. Nos. 60/215,456, 60/170,175, and 60/393,862. Thedisclosures of all of the preceding patents and patent applications areincorporated by reference herein in their entirety. These catalysts tendto have a higher molecular weight capability.

Other catalysts, cocatalysts, catalyst systems, and activatingtechniques which may be used in the practice of the invention disclosedherein may include those disclosed in WO 96/23010, published on Aug. 1,1996, the entire disclosure of which is hereby incorporated byreference; those disclosed in WO 99/14250, published Mar. 25, 1999, theentire disclosure of which is hereby incorporated by reference; thosedisclosed in WO 98/41529, published Sep. 24, 1998, the entire disclosureof which is hereby incorporated by reference; those disclosed in WO97/42241, published Nov. 13, 1997, the entire disclosure of which ishereby incorporated by reference; those disclosed by Scollard, et al.,in J. Am. Chem. Soc 1996, 118, 10008–10009, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in EP 0 468537 B1, published Nov. 13, 1996, the entire disclosure of which ishereby incorporated by reference; those disclosed in WO 97/22635,published Jun. 26, 1997, the entire disclosure of which is herebyincorporated by reference; those disclosed in EP 0 949 278 A2, publishedOct. 13, 1999, the entire disclosure of which is hereby incorporated byreference; those disclosed in EP 0 949 279 A2, published Oct. 13, 1999,the entire disclosure of which is hereby incorporated by reference;those disclosed in EP 1 063 244 A2, published Dec. 27, 2000, the entiredisclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 5,408,017, the entire disclosure of which is herebyincorporated by reference; those disclosed in U.S. Pat. No. 5,767,208,the entire disclosure of which is hereby incorporated by reference;those disclosed in U.S. Pat. No. 5,907,021, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in WO88/05792, published Aug. 11, 1988, the entire disclosure of which ishereby incorporated by reference; those disclosed in WO 88/05793,published Aug. 11, 1988, the entire disclosure of which is herebyincorporated by reference; those disclosed in WO 93/25590, publishedDec. 23, 1993, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,599,761, the entiredisclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 5,218,071, the entire disclosure of which is herebyincorporated by reference; those disclosed in WO 90/07526, publishedJul. 12, 1990, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,972,822, the entiredisclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 6,074,977, the entire disclosure of which is herebyincorporated by reference; those disclosed in U.S. Pat. No. 6,013,819,the entire disclosure of which is hereby incorporated by reference;those disclosed in U.S. Pat. No. 5,296,433, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in U.S. Pat.No. 4,874,880, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,198,401, the entiredisclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 5,621,127, the entire disclosure of which is herebyincorporated by reference; those disclosed in U.S. Pat. No. 5,703,257,the entire disclosure of which is hereby incorporated by reference;those disclosed in U.S. Pat. No. 5,728,855, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in U.S. Pat.No. 5,731,253, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,710,224, the entiredisclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 5,883,204, the entire disclosure of which is herebyincorporated by reference; those disclosed in U.S. Pat. No. 5,504,049,the entire disclosure of which is hereby incorporated by reference;those disclosed in U.S. Pat. No. 5,962,714, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in U.S. Pat.No. 5,965,677, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,427,991, the entiredisclosure of which is hereby incorporated by reference; those disclosedin WO 93/21238, published Oct. 28, 1993, the entire disclosure of whichis hereby incorporated by reference; those disclosed in WO 94/03506,published Feb. 17, 1994, the entire disclosure of which is herebyincorporated by reference; those disclosed in WO 93/21242, publishedOct. 28, 1993, the entire disclosure of which is hereby incorporated byreference; those disclosed in WO 94/00500, published Jan. 6, 1994, theentire disclosure of which is hereby incorporated by reference; thosedisclosed in WO 96/00244, published Jan. 4, 1996, the entire disclosureof which is hereby incorporated by reference; those disclosed in WO98/50392, published Nov. 12, 1998, the entire disclosure of which ishereby incorporated by reference; those disclosed in Wang, et al.,Organometallics 1998, 17, 3149–3151, the entire disclosure of which ishereby incorporated by reference; those disclosed in Younkin, et al.,Science 2000, 287, 460-462, the entire disclosure of which is herebyincorporated by reference; those disclosed by Chen and Marks, Chem. Rev.2000, 100, 1391–1434, the entire disclosure of which is herebyincorporated by reference; those disclosed by Alt and Koppl, Chem. Rev.2000, 100, 1205–1221, the entire disclosure of which is herebyincorporated by reference; those disclosed by Resconi, et al., Chem.Rev. 2000, 100, 1253–1345, the entire disclosure of which is herebyincorporated by reference; those disclosed by Ittel, et al., Chem. Rev.2000, 100, 1169–1203, the entire disclosure of which is herebyincorporated by reference; those disclosed by Coates, Chem. Rev., 2000,100, 1223–1251, the entire disclosure of which is hereby incorporated byreference; those disclosed by Brady, III, et al., U.S. Pat. No.5,093,415, the entire disclosure of which is hereby incorporated byreference, those disclosed by Murray, et al., U.S. Pat. No. 6,303,719,the entire disclosure of which is hereby incorporated by reference,those disclosed by Saito, et al., U.S. Pat. No. 5,874,505, the entiredisclosure of which is hereby incorporated by reference; and thosedisclosed in WO 96/13530, published May 9, 1996, the entire disclosureof which is hereby incorporated by reference. Also useful are thosecatalysts, cocatalysts, and catalyst systems disclosed in U.S. Ser. No.09/230,185, filed Jan. 15, 1999; U.S. Pat. No. 5,965,756; U.S. Pat. No.6,150,297; U.S. Ser. No. 09/715,380, filed Nov. 17, 2000.

Process Descriptions

In one embodiment, the process reagents, i.e., (i) propylene, (ii)ethylene and/or one or more unsaturated comonomers, (iii) catalyst, and,(iv) optionally, solvent and/or a molecular weight regulator (e.g.,hydrogen), are fed to a single reaction vessel of any suitable design,e.g., stirred tank, loop, fluidized-bed, etc. The process reagents arecontacted within the reaction vessel under appropriate conditions (e.g.,solution, slurry, gas phase, suspension, high pressure) to form thedesired polymer, and then the output of the reactor is recovered forpost-reaction processing. All of the output from the reactor can berecovered at one time (as in the case of a single pass or batchreactor), or it can be recovered in the form of a bleed stream whichforms only a part, typically a minor part, of the reaction mass (as inthe case of a continuous process reactor in which an output stream isbled from the reactor at the same rate at which reagents are added tomaintain the polymerization at steady-state conditions). “Reaction mass”means the contents within a reactor, typically during or subsequent topolymerization. The reaction mass includes reactants, solvent (if any),catalyst, and products and by-products. The recovered solvent andunreacted monomers can be recycled back to the reaction vessel.

The polymerization conditions at which the reactor is operated aresimilar to those for the polymerization of propylene using a known,conventional Ziegler-Natta catalyst. Typically, solution polymerizationof propylene is performed at a polymerization temperature between about−50 to about 200, preferably between about −10 and about 150 C, and morepreferably between about 20 to about 150 C and most preferably betweenabout 80 and 150 C, and the polymerization pressure is typically betweenabout atmospheric to about 7, preferably between about 0.2 and about 5,Mpa. If hydrogen is present, then it is usually present at a partialpressure (as measured in the gas phase portion of the polymerization) ofabout 0.1 kPa to about 5 Mpa, preferably between about 1 kPa to about 3Mpa. Gas phase, suspension and other polymerization schemes will useconditions conventional for those schemes. For gas-phase or slurry-phasepolymerization processes, it is desirable to perform the polymerizationat a temperature below the melting point of the polymer.

For the propylene/ethylene copolymer processes described herein,optionally containing additional unsaturated monomer, the weight ratioof propylene to ethylene in the feed to the reactors is preferably inthe range of 10,000:1 to 1:10, more preferably 1,000:1 to 1:1, stillmore preferably 500:1 to 3:1. For the propylene/C₄₋₂₀ α-olefin copolymerprocesses of the present invention, the weight ratio of propylene toC₄₋₂₀ α-olefin in the feed preferably is in the range of 10,000:1 to1:20, more preferably 1,000:1 to 1:1, still more preferably 1,000:1 to3:1.

The post-reactor processing of the recover reaction mass from thepolymerization vessel typically includes the deactivation of thecatalyst, removal of catalyst residue, drying of the product, and thelike. The recovered polymer is then ready for storage and/or use.

The propylene copolymer produced in a single reaction vessel inaccordance with this invention will have the desired MFR, narrow MWD,¹³C NMR peaks at 14.6 and 15.7 ppm (the peaks of approximately equalintensity), a high B-value, and its other defining characteristics. If,however, a broader MWD is desired, e.g., a MWD of between about 2.5 andabout 3.5 or even higher, without any substantial change to the otherdefining characteristics of the propylene copolymer, then the copolymeris preferably made in a multiple reactor system. In multiple reactorsystems, MWD as broad as 15, more preferably 10, most preferably 4–8,can be prepared.

Preferably, to obtain a broad MWD, at least two of the catalysts used ina single reactor have a high weight-average molecular weight(M_(wH))/low weight average molecular weight (M_(wL)) ratio(M_(wH)/M_(wL), as defined later) in the range from about 1.5 to about10, and the process used is a gas phase, slurry, or solution process.More preferably, at least two of the catalysts used in a single reactorhave M_(wH)/M_(wL) in the range from about 1.5 to about 10, and theprocess used is a continuous solution process, especially a continuoussolution process wherein the polymer concentration in the reactor atsteady state is at least 15% by weight of the reactor contents. Stillmore preferably, at least two of the catalysts used in a single reactorhave M_(wH)/M_(wL) in the range from about 1.5 to about 10, and theprocess used is a continuous solution process wherein the polymerconcentration in the reactor at steady state is at least 18% by weightof the reactor contents. Most preferably, at least two of the catalystsused in a single reactor have M_(wH)/M_(wL) in the range from about 1.5to about 10, and the process used is a continuous solution processwherein the polymer concentration in the reactor at steady state is atleast 20% by weight of the reactor contents.

In one embodiment, the monomers comprise propylene and at least oneolefin selected from the group consisting of C₄–C₁₀ α-olefins,especially 1-butene, 1-hexene, and 1-octene, and the melt flow rate(MFR) of the interpolymer is preferably in the range of about 0.1 toabout 500, more preferably in the range from about 0.1 to about 100,further more preferably about 0.2 to 80, most preferably in the range of0.3–50. In some embodiments, the nonmetallocene, catalysts used in thepractice of the invention described herein may be utilized incombination with at least one additional homogeneous or heterogeneouspolymerization catalyst in separate reactors connected in series or inparallel to prepare polymer blends having desirable properties. Anexample of such a process is disclosed in WO 94/00500, equivalent toU.S. Ser. No. 07/904,770, as well as U.S. Ser. No. 08/10958, filed Jan.29, 1993. Included in these embodiments is the use of two differentnonmetallocene, metal-centered, heteroaryl ligand catalysts.

The catalyst system may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent in whichpolymerization will be carried out by solution polymerizationprocedures. The catalyst system may also be prepared and employed as aheterogeneous catalyst by adsorbing the requisite components on acatalyst support material such as silica gel, alumina or other suitableinorganic support material. When prepared in heterogeneous or supportedform, it is preferred to use silica as the support material. Theheterogeneous form of the catalyst system may be employed in a slurry orgas phase polymerization. As a practical limitation, slurrypolymerization takes place in liquid diluents in which the polymerproduct is substantially insoluble. Preferably, the diluent for slurrypolymerization is one or more hydrocarbons with less than 5 carbonatoms. If desired, saturated hydrocarbons such as ethane, propane orbutane may be used in whole or part as the diluent. Likewise theα-olefin comonomer or a mixture of different α-olefin comonomers may beused in whole or part as the diluent. Most preferably, the major part ofthe diluent comprises at least the α-olefin monomer or monomers to bepolymerized.

Solution polymerization conditions utilize a solvent for the respectivecomponents of the reaction. Preferred solvents include, but are notlimited to, mineral oils and the various hydrocarbons which are liquidat reaction temperatures and pressures. Illustrative examples of usefulsolvents include, but are not limited to, alkanes such as pentane,iso-pentane, hexane, heptane, octane and nonane, as well as mixtures ofalkanes including kerosene and Isopar E™, available from Exxon ChemicalsInc.; cycloalkanes such as cyclopentane, cyclohexane, andmethylcyclohexane; and aromatics such as benzene, toluene, xylenes,ethylbenzene and diethylbenzene.

At all times, the individual ingredients, as well as the catalystcomponents, should be protected from oxygen and moisture. Therefore, thecatalyst components and catalysts should be prepared and recovered in anoxygen and moisture free atmosphere. Preferably, therefore, thereactions are performed in the presence of a dry, inert gas such as, forexample, nitrogen or argon.

The polymerization may be carried out as a batch or a continuouspolymerization process. A continuous process is preferred, in whichevent catalysts, solvent or diluent (if employed), and comonomers (ormonomer) are continuously supplied to the reaction zone and polymerproduct continuously removed therefrom. The polymerization conditionsfor manufacturing the interpolymers according to embodiments of theinvention are generally those useful in the solution polymerizationprocess, although the application is not limited thereto. Gas phase andslurry polymerization processes are also believed to be useful, providedthe proper catalysts and polymerization conditions are employed.

In some embodiments, the polymerization is conducted in a continuoussolution polymerization system comprising two or more reactors connectedin series or parallel. A catalyst solution comprising a nonmetallocene,metal-centered, heteroaryl ligand catalyst as described previously isused to polymerize propylene and optionally additional olefin monomersin at least one reactor. In one reactor, a relatively high molecularweight product (M_(w), from 100,000 to over 1,000,000, more preferably200,000 to 500,000) is formed while in the second or subsequentreactor(s) a product of a relatively low molecular weight (M_(w)2,000 to300,000) is formed. The final product is a mixture of the two reactoreffluents which are combined prior to devolatilization to result in auniform mixing of the two polymer products. Such a dual reactor/dualcatalyst process allows for the preparation of products with tailoredproperties.

In one embodiment, the reactors are connected in series, that is theeffluent from the first reactor is charged to the second reactor andfresh monomer(s), solvent and hydrogen is added to the second reactor.Reactor conditions are adjusted such that the weight ratio of polymerproduced in the first reactor to that produced in the second reactortypically from about 20:80 to about 80:20. Preferably, the weight ratioof polymer produced in the first reactor to that produced in the secondreactor is from about 25:75 to about 75:25, more preferably from about30:70 to about 70:30.

One representative example of a series polymerization is the preparationof propylene copolymer in which in the first reactor, propylene,ethylene, solvent and catalyst are contacted under solution phaseconditions such that the propylene and ethylene copolymerize to formpropylene copolymer. The catalyst used in the practice of thisinvention, however, is highly active and under appropriate conditions,converts 50% or more of the propylene and virtually all of the ethyleneto the copolymer. Consequently when the contents, i.e., reaction mass,of the first reactor is transferred to the second reactor, most, if notall, of the polymer made in the second reactor is propylene homopolymerdue to the absence or near absence of ethylene comonomer to the secondreactor. One skill in the art understands that many variations on thistheme are possible by replacing ethylene with, or using in combinationwith ethylene, one or more unsaturated comonomers; using a second butrelated catalyst in the second reactor; etc.

In one embodiment, the second reactor in a series polymerization processcontains a heterogeneous Ziegler-Natta catalyst or chrome catalyst knownin the art. Examples of Ziegler-Natta catalysts include, but are notlimited to, titanium-based catalysts supported on MgCl₂, andadditionally comprise compounds of aluminum containing at least onealuminum-alkyl bond. Suitable Ziegler Natta catalysts and theirpreparation include, but are not limited to, those disclosed in U.S.Pat. Nos. 4,612,300, 4,330,646 and 5,869,575. In another embodiment ofthe present invention, the second reactor in a series polymerizationprocess contains a constrained geometry or a bis-Cp metallocenecatalyst.

In another embodiment of this invention, propylene/ethylene copolymersare prepared in high yield and productivity. The process employed tomake these copolymers may be either a solution or slurry process both ofwhich are known in the art. Kaminsky, J. Poly. Sci., Vol. 23, pp.2151–64 (1985) reported the use of a soluble bis(cyclopentadienyl)zirconium dimethyl-alumoxane catalyst system for solution polymerizationof propylene/ethylene (PE) elastomers. U.S. Pat. No. 5,229,478 disclosesa slurry polymerization process utilizing similar bis(cyclopentadienyl)zirconium based catalyst systems.

The following procedure may be carried out to obtain a P/E* copolymer:In a stirred-tank reactor propylene monomer is introduced continuouslytogether with solvent, and ethylene monomer. The reactor contains aliquid phase composed substantially of ethylene and propylene monomerstogether with any solvent or additional diluent. If desired, a smallamount of a “H”-branch inducing diene such as norbornadiene,1,7-octadiene or 1,9-decadiene may also be added. A nonmetallocene,metal-centered, heteroaryl ligand catalyst and suitable cocatalyst arecontinuously introduced in the reactor liquid phase. The reactortemperature and pressure may be controlled by adjusting thesolvent/monomer ratio, the catalyst addition rate, as well as by coolingor heating coils, jackets or both. The polymerization rate is controlledby the rate of catalyst addition. The ethylene content of the polymerproduct is determined by the ratio of ethylene to propylene in thereactor, which is controlled by manipulating the respective feed ratesof these components to the reactor. The polymer product molecular weightis controlled, optionally, by controlling other polymerization variablessuch as the temperature, monomer concentration, or by a stream ofhydrogen introduced to the reactor, as is known in the art. The reactoreffluent is contacted with a catalyst kill agent, such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off unreacted gaseous ethylene and propylene aswell as residual solvent or diluent at reduced pressure, and, ifnecessary, conducting further devolatilization in equipment such as adevolatilizing extruder or other devolatilizing equipment operated atreduced pressure. For a solution polymerization process, especially acontinuous solution polymerization, preferred ranges of propyleneconcentration at steady state are from about 0.05 weight percent of thetotal reactor contents to about 50 weight percent of the total reactorcontents, more preferably from about 0.5 weight percent of the totalreactor contents to about 30 weight percent of the total reactorcontents, and most preferably from about 1 weight percent of the totalreactor contents to about 25 weight percent of the total reactorcontents. The preferred range of polymer concentration (otherwise knownas % solids) is from about 3% of the reactor contents by weight to about45% of the reactor contents or higher, more preferably from about 10% ofthe reactor contents to about 40% of the reactor contents, and mostpreferably from about 15% of the reactor contents to about 40% of thereactor contents.

In a continuous process, the mean residence time of the catalyst andpolymer in the reactor generally is from 5 minutes to 8 hours, andpreferably from 10 minutes to 6 hours, more preferably from 10 minutesto 1 hour.

In some embodiments, ethylene is added to the reaction vessel in anamount to maintain a differential pressure in excess of the combinedvapor pressure of the propylene and diene monomers. The ethylene contentof the polymer is determined by the ratio of ethylene differentialpressure to the total reactor pressure. Generally the polymerizationprocess is carried out with a pressure of ethylene of from 10 to 1000psi (70 to 7000 kPa), most preferably from 40 to 800 psi (30 to 600kPa). The polymerization is generally conducted at a temperature of from25 to 250° C., preferably from 75 to 200° C., and most preferably fromgreater than 95 to 200° C.

In another embodiment of the invention, a process for producing apropylene homopolymer or interpolymer of propylene with at least oneadditional olefinic monomer selected from ethylene or C₄₋₂₀ α-olefinscomprises the following steps: 1) providing controlled addition of anonmetallocene, metal-centered, heteroaryl ligand catalyst to a reactor,including a cocatalyst and optionally a scavenger component; 2)continuously feeding propylene and optionally one or more additionalolefinic monomers independently selected from ethylene or C₄₋₂₀α-olefins into the reactor, optionally with a solvent or diluent, andoptionally with a controlled amount of H₂; and 3) recovering the polymerproduct. Preferably, the process is a continuous solution process. Thecocatalysts and optional scavenger components in the novel process canbe independently mixed with the catalyst component before introductioninto the reactor, or they may each independently be fed into the reactorusing separate streams, resulting in “in reactor” activation. Scavengercomponents are known in the art and include, but are not limited to,alkyl aluminum compounds, including alumoxanes. Examples of scavengersinclude, but are not limited to, trimethyl aluminum, triethyl aluminum,triisobutyl aluminum, trioctyl aluminum, methylalumoxane (MAO), andother alumoxanes including, but not limited to, MMAO-3A, MMAO-7, PMAO-IP(all available from Akzo Nobel).

As previously note, the process described above may optionally use morethan one reactor. The use of a second reactor is especially useful inthose embodiments in which an additional catalyst, especially aZiegler-Natta or chrome catalyst, or a metallocene catalyst, especiallya CGC, is employed. The second reactor typically holds the additionalcatalyst.

By proper selection of process conditions, including catalyst selection,polymers with tailored properties can be produced. For a solutionpolymerization process, especially a continuous solution polymerization,preferred ranges of ethylene concentration at steady state are from lessthan about 0.02 weight percent of the total reactor contents to about 5weight percent of the total reactor contents, and the preferred range ofpolymer concentration is from about 10% of the reactor contents byweight to about 45% of the reactor contents or higher.

In general, catalyst efficiency (expressed in terms of gram of polymerproduced per gram of transition metal) decreases with increasingtemperature and decreasing ethylene concentration. In addition, themolecular weight of the polymer product generally decreases withincreasing reactor temperature and decreases with decreasing propyleneand ethylene concentration. The molecular weight of the polyolefin canalso be controlled with the addition of chain transfer compounds,especially through the addition of H₂.

When two or more different catalysts are used in certain embodimentsdisclosed herein, each catalyst may make a different molecular weightproduct. A high molecular weight catalyst is defined relative to a lowmolecular weight catalyst. A high weight molecular weight catalystrefers to a catalyst which by itself produces a polymer with a highweight-average molecular weight M_(wH) from the comonomers of choiceunder a set of given polymerization conditions, whereas a low molecularweight catalyst refers to a catalyst which by itself produces a polymerwith a low weight average molecular weight M_(wL) from the samecomonomers under substantially the same polymerization conditions.Moreover, the ratio of the high molecular weight to the low molecularweight, i.e., M_(wH)/M_(wL) is greater than about 1.3. Generally, theratio, M_(wH)/M_(wL), is in the range from about 1.5 to about 60,preferably in the range from about 1.5 to about 40, and more preferablyfrom about 1.5 to about 10. In some embodiments, the ratio is from about3.0 to about 6.0. In other embodiments, the ratio M_(wH)/M_(wL) can begreater than 60 (e.g., 70, 80, 90, or even 100), but it is generallyless preferred.

Due to the intrinsic molecular weight differences in the polymerproduced by the chosen high and low molecular weight catalysts, thepolymer produced by the two catalysts in a single reactor has a highmolecular weight fraction and a low molecular weight fraction. Such aphenomenon is referred to herein after as “polymer split.” A polymermolecular weight split is defined as the weight fraction of the highmolecular weight polymer component or fraction in a polymer with suchsplit. The relative fraction of the high molecular weight component canbe measured by deconvoluting a gel permeation chromatography (“GPC”)peak. One characteristic of the process described herein is that thepolymer molecular weight split may be varied from 0 to 100% by adjustingthe ratio of the high molecular weight catalyst to the low molecularweight catalyst. Because any two catalysts may exhibit differentcatalytic efficiency at a given set of polymerization processconditions, the polymer molecular weight split may not corresponddirectly to the molar ratio of the two catalysts.

A high molecular weight catalyst and a low molecular weight catalyst aredetermined with reference to each other. One does not know whether acatalyst is a high molecular weight catalyst or a low molecular weightcatalyst until after another catalyst is also selected. Therefore, theterms “high molecular weight” and “low molecular weight” used hereinwhen referring to a catalyst are merely relative terms and do notencompass any absolute value with respect to the molecular weight of apolymer. After a pair of catalysts are selected, one can easilyascertain which one is the high molecular catalyst by the followingprocedure: 1) select at least one monomer which can be polymerized bythe chosen catalysts; 2) make a polymer from the selected monomer(s) ina single reactor containing one of the selected catalysts underpre-selected polymerization conditions; 3) make another polymer from thesame monomer(s) in a single reactor containing the other catalyst undersubstantially the same polymerization conditions; and 4) measure the MFRfor the respective interpolymers. The catalyst that yields a lower MFRis the higher molecular weight catalyst. Conversely, the catalyst thatyields a high MFR is the lower molecular weight catalyst. Using thismethodology, it is possible to rank a plurality of catalysts based onthe molecular weight of the polymers they can produce undersubstantially the same conditions. As such, one may select three, four,five, six, or more catalysts according their molecular weight capabilityand use these catalysts simultaneously in a single polymerizationreactor to produce polymers with tailored structures and properties.

The nature of the polymer product of the instant invention depends onthe characteristics of each catalyst as well as the specifics of theprocess in which the catalysts are used. By careful choice of eachcatalyst, the polymer product can be tailored to achieve specificproperties. For example, in order to obtain a polymer with a broadermolecular weight distribution, two (or more) catalysts preferably shouldbe chosen so that the difference in molecular weight at the conditionsof polymerization (M_(wH)/M_(wL)) is large, preferably greater than 4.0,more preferably greater than 6.0, even more preferably greater than 8.0.For a narrower MWD product, the catalysts preferably should be chosen sothat M_(wH)/M_(wL) is relatively low, preferably 4.0 or less, morepreferably 3.0 or less, still more preferably 2.5 or less.

In one embodiment of the invention, a process for producing a propylenehomopolymer or interpolymer of propylene with at least one additionalolefinic monomer selected from ethylene or C₄₋₂₀ α-olefins comprises thefollowing steps: 1) providing controlled addition of a nonmetallocene,metal-centered, pyridyl-amine catalyst to a reactor, including acocatalyst and optionally a scavenger component; 2) continuously feedingpropylene and optionally one or more additional olefinic monomersindependently selected from ethylene or C₄₋₂₀ α-olefins into thereactor, optionally with a solvent or diluent, and optionally with acontrolled amount of H₂, 3) feeding a second catalyst to the samereactor, including a cocatalyst and optionally a scavenger; and 4)recovering the polymer product. Preferably, the process is a continuoussolution process. The cocatalysts and optional scavenger components inthe novel process can be independently mixed with each catalystcomponent before introduction into the reactor, or they may eachindependently be fed into the reactor using separate streams, resultingin “in reactor” activation. The novel process described above mayoptionally use more than one reactor, especially where a second reactoris used wherein the second reactor comprises an additional catalyst,especially a Ziegler-Natta or chrome catalyst, a metallocene catalyst,especially a CGC.

Applications

The polymers made in accordance with embodiments of the invention havemany useful applications. For example, fabricated articles made from thepolymers may be prepared using all of the conventional polyolefinprocessing techniques. Useful articles include films (e.g., cast, blown,calendaring and extrusion coated), including multi-layer films,greenhouse films, shrink films including clarity shrink film, laminationfilm, biaxially-oriented film, extrusion coating, liners, clarityliners, overwrap film, agricultural film; fibers (e.g., staple fibers)including use of an interpolymer disclosed herein as at least onecomponent comprising at least a portion of the fiber's surface),spunbond fibers or melt blown fibers (using, e.g., systems as disclosedin U.S. Pat. Nos. 4,430,563, 4,663,220, 4,668,566 or 4,322,027), and gelspun fibers (e.g., the system disclosed in U.S. Pat. No. 4,413,110);both woven and nonwoven fabrics (e.g., spunlaced fabrics disclosed inU.S. Pat. No. 3,485,706) or structures made from such fibers (including,e.g., blends of these fibers with other fibers such as PET or cotton),foams, and thermoform and molded articles (e.g., made using an injectionmolding process, a blow molding process or a rotomolding process).Monolayer and multilayer films may be made according to the filmstructures and fabrication methods described in U.S. Pat. No. 5,685,128.

The inventive polymers exhibit excellent optics. FIG. 10 illustrates theimproved haze values reported by compression molded films made from theinventive polymer versus a similar film made from a comparablemetallocene catalyzed propylene polymer across various ethylenecontents. Similar films also demonstrate comparable haze values measuredacross various T_(max) (FIG. 11), and improved flexibility measuredacross both ethylene content and T_(max) (FIGS. 12 and 13). The databehind these figures is reported in Example 21.

The polymers of this invention also exhibit excellent elasticity. FIG.14 reports the comparative results for elasticity of two copolymers ofthis invention at different ethylene contents versus a metallocenecatalyzed propylene copolymer, a polyethylene elastomer, andethylene-styrene elastomer and a hydgrogenatedstyrene-ethylene-butene-styrene block elastomer. Of even more interest,FIG. 15 reports the comparative results of these same elastomers afterbeing stretched. The elasticity of the polymers of this invention notonly increased markedly, but they now compared favorably even to thehydgrogenated styrene-ethylene-butene-styrene block elastomers. The databehind these figures is reported in Example 22. FIG. 32 reports anelasticity-modulus relationship for metallocene-catalyzed andnonmetallocene-catalyzed polymers. The data of these figures show thatthe nonmetallocene-catalyzed copolymers have higher modulus at the sameelasicity, both pre- and post-stretched. This means that less materialis needed of the nonmetallocene-catalyzed polymer than themetallocene-catalyzed polymer for the same elastic performance.

The elastomeric polymers of this invention can be used in a variety ofdifferent applications including fiber, film, sheeting and moldedarticles. Whether or not pre-stretching is desirable will depend uponthe application. For example, the elastomeric polymers of this inventioncan replace the thermoplastic triblock elastomers as the filament layerin the stretch bonded laminate process of U.S. Pat. No. 6,323,389. Thefilament layer would be stretched, preferably only once, prior to beingsandwiched between the two spunbond layers. In an alternative example,the elastomeric polymers of this invention can replace the elastic layerin the necked bonded laminate process of U.S. Pat. No. 5,910,224. Somepre-stretching of the propylene polymer may be preferred.

With respect to injection molding applications, the polymers of thisinvention exhibit a good balance between low haze values and toughness.For example, a comparison of samples 19-1-1 and 19-1-2 in Table 19-1shows that at the same level of haze (e.g., a relatively low 11%) theinventive polymers exhibit an equivalent modulus and a better toughnessthan a comparable propylene-ethylene-octene polymer made with ametallocene catalyst. Moreover, at a similar level of haze the inventivepolymers are almost an order of magnitude more flexible and much tougherthan a comparable Ziegler-Natta catalyzed propylene-ethylene polymer. Incomparison to ethylene-octene polymers, comparable inventive polymersdisplay a higher flexural modulus and hardness at equivalent upperservice temperatures, e.g., >70 C. These properties, in turn, mean thatthe inventive polymers are useful in various film and impactapplications, e.g., packaging and facia.

With respect to blown film applications, the inventive polymers exhibitexcellent optics, e.g., low haze and high gloss, and much bettertoughness (e.g., tear and dart) than traditional Ziegler-Natta catalyzedpolypropylene at comparable ethylene contents. These are characteristicsare shown in FIGS. 16–18. Moreover, blown films made from the inventivepolymers exhibit excellent hot tack and heat seal properties (e.g., abroader temperature window for the former and a lower sealingtemperature for the latter than comparable Ziegler-Natta catalyzedpolypropylene, even when the latter has a higher ethylene content).FIGS. 19 and 20 illustrate these properties. The inventive polymers alsoexhibit superior toughness and haze and gloss at equivalent modulus thanmany traditional polyethylenes, e.g., linear low density polyethylene,and certain polyethylene blends, e.g., in-reactor blends of at least onemetallocene catalyzed polyethylene and at least one Ziegler-Nattacatalyzed polyethylene. The experimental details behind the data ofthese figures is reported in Example 20.

The polymers of this invention are also useful for wire and cablecoating operations, wire and cable jacketing, including low, medium andhigh voltage cable jacketing, semi-conductive layers used in wire andcable power applications, wire and cable insulation, especially mediumand high voltage cable insulation, telecommunications cable jackets,optical fiber jackets, as well as in sheet extrusion for vacuum formingoperations. In addition, the novel polymers may be used in foams,including high strength foam, soft foam, rigid foam, cross-linked foam,high strength foam for cushioning applications, and sound insulationfoam, blow molded bottles, frozen food packages; thermoforming,especially cups and plates, trays and containers; injection moulding;blow-moulding; pipe, including potable water pipe and high pressurepipe; and automotive parts. The skilled artisan will appreciate otheruses for the novel polymers and compositions disclosed herein.

Useful compositions are also suitably prepared comprising the polymersaccording to embodiments of the invention and at least one other naturalor synthetic polymer. Preferred other polymers include, but are notlimited to, thermoplastics, such as styrene-butadiene block copolymers,polystyrene (including high impact polystyrene), ethylene vinyl alcoholcopolymers, ethylene acrylic acid copolymers, other olefin copolymers(especially polyethylene copolymers) and homopolymers (e.g., those madeusing conventional heterogeneous catalysts). Examples include polymersmade by the process of U.S. Pat. No. 4,076,698, other linear orsubstantially linear polymers as described in U.S. Pat. No. 5,272,236,and mixtures thereof. Other substantially linear polymers andconventional HDPE and/or LDPE may also be used in the thermoplasticcompositions.

Melt Strength (measured in cN) and Melt Drawability (measured in mm/s)are measured by pulling strands of the molten polymers or blends atconstant acceleration until breakage occurs. The experimental set-upconsists of a capillary rheometer and a Rheotens apparatus as take-updevice. The molten strand is drawn uniaxially to a set of acceleratingnips located 100 mm below the die. The force required to uniaxiallyextend the strands is recorded as a function of the take-up velocity ofthe nip rolls. In the case of polymer melts exhibiting draw resonance(indicated by the onset of a periodic oscillation of increasingamplitude in the measured force profile), the maximum force and wheelvelocity before the onset of draw resonance are taken as the meltstrength and drawability, respectively. In the absence of drawresonance, the maximum force attained during test is defined as the meltstrength and the velocity at which breakage occurs is defined as themelt drawability. These tests are run under the following conditions:

TABLE F Melt Strength and Drawablility Test Conditions Mass flow rate: 1.35 gram/min Temperature: 190° C. Equilibration Time at 190° C.: 10minutes Die: 20:1 with entrance angle of aproximately 45 degreesCapillary length:  41.9 mm Capillary diameter:  2.1 mm Piston diameter: 9.54 mm Piston velocity: 0.423 mm/s Shear rate:  33.0 S⁻¹ Draw-downdistance (die exit to take-up wheels):   100 mm Cooling conditions:ambient air Acceleration:  2.4 mm/s²

For one aspect of the present invention, the novel polymers are usefulto produce foams having improved properties. For foams, and otherapplications requiring melt strength, the MFR is preferably in the rangeof 0.1–10, more preferably 0.3–3, most preferably 0.5–2. The meltstrength is preferably greater than 5 cN, more preferably >9 cN, mostpreferably >12 Cn. The drawability is preferably >15 mm/sec, morepreferably >25 mm/sec, most preferably >35 mm/sec.

In one aspect of the present invention, the novel polymers disclosed inthe present invention are useful for a wide range of applications wheregood optical properties are beneficial. Gloss is measured according toASTM D-1746. Haze is measured according to ASTM D-1003, and Clarity ismeasured according to ASTM D-2457. In one aspect of the polymersdisclosed herein, films having haze of less than 10% can be produced. Inaddition films having clarity of >91% are beneficially obtained.

The polymers of this invention, either alone or in combination with oneor more other polymers (either polymers of the invention or polymers notof the invention) may be blended, if desired or necessary, with variousadditives such as antioxidants, ultraviolet absorbing agents, antistaticagents, nucleating agents, lubricants, flame retardants, antiblockingagents, colorants, inorganic or organic fillers or the like.

As noted above, the polymers of this invention are useful in thepreparation of fibers and films. With respect to fibers, elastic fiberscomprising polyolefins are known, e.g., U.S. Pat. Nos. 5,272,236,5,278,272, 5,322,728, 5,380,810, 5,472,775, 5,645,542, 6,140,442 and6,225,243. The polymers of this invention can be used in essentially thesame manner as known polyolefins for the making and using of elasticfibers. In this regard, the polymers of this invention can includefunctional groups, such as a carbonyl, sulfide, silane radicals, etc.,and can be crosslinked or uncrosslinked. If crosslinked, the polymerscan be crosslinked in any known manner, e.g., peroxide, azo,electromagnetic radiation such as electron beam, UV, IR, visible light,and the like. The use of additives, promoters, etc., can be employed asdesired.

The polypropylene polymers of this invention can be blended with otherpolymers to form, among other things, useful fibers. Suitable polymersfor blending with the polypropylene polymers of this invention arecommercially available from a variety of suppliers and include, but arenot limited to, other polyolefins such as an ethylene polymer (e.g., lowdensity polyethylene (LDPE), ULDPE, medium density polyethylene (MDPE),LLDPE, HDPE, homogeneously branched linear ethylene polymer,substantially linear ethylene polymer, graft-modified ethylene polymerethylene-styrene interpolymers, ethylene vinyl acetate interpolymer,ethylene acrylic acid interpolymer, ethylene ethyl acetate interpolymer,ethylene methacrylic acid interpolymer, ethylene methacrylic acidionomer, and the like), polycarbonate, polystyrene, conventionalpolypropylene (e.g., homopolymer polypropylene, polypropylene copolymer,random block polypropylene interpolymer and the like), thermoplasticpolyurethane, polyamide, polylactic acid interpolymer, thermoplasticblock polymer (e.g. styrene butadiene copolymer, styrene butadienestyrene triblock copolymer, styrene ethylene-butylene styrene triblockcopolymer and the like), polyether block copolymer (e.g., PEBAX),copolyester polymer, polyester/polyether block polymers (e.g., HYTEL),ethylene carbon monoxide interpolymer (e.g., ethylene/carbon monoxide(ECO), copolymer, ethylene/acrylic acid/carbon monoxide (EAACO)terpolymer, ethylene/methacrylic acid/carbon monoxide (EMAACO)terpolymer, ethylene/vinyl acetate/carbon monoxide (EVACO) terpolymerand styrene/carbon monoxide (SCO)), polyethylene terephthalate (PET),chlorinated polyethylene, and the like and mixtures thereof. In otherwords, the polyolefin used in the practice of this invention can be ablend of two or more polyolefins, or a blend of one or more polyolefinswith one or more polymers other than a polyolefin. If the polyolefinused in the practice of this invention is a blend of one or morepolyolefins with one or more polymers other than a polyolefin, then thepolyolefins comprise at least about 1, preferably at least about 50 andmore preferably at least about 90, wt % of the total weight of theblend.

In one embodiment, one or more polypropylene polymers of this inventionis blended with a conventional polypropylene polymer. Suitableconventional polypropylene polymers for use in the invention, includingrandom propylene ethylene polymers, are available from a number ofmanufacturers, such as, for example, Montell Polyolefins and ExxonChemical Company. Suitable conventional polypropylene polymers fromExxon are supplied under the designations ESCORENE and ACHIEVE.

Suitable graft-modified polymers for use in this invention are wellknown in the art, and include the various ethylene polymers bearing amaleic anhydride and/or another carbonyl-containing, ethylenicallyunsaturated organic radical. Representative graft-modified polymers aredescribed in U.S. Pat. No. 5,883,188, such as a homogeneously branchedethylene polymer graft-modified with maleic anhydride.

Suitable polylactic acid (PLA) polymers for use in the invention arewell known in the literature (e.g., see D. M. Bigg et al., “Effect ofCopolymer Ratio on the Crystallinity and Properties of Polylactic AcidCopolymers”, ANTEC '96, pp. 2028–2039; WO 90/01521; EP 0 515 203A and EP0 748 846 A2. Suitable polylactic acid polymers are suppliedcommercially by Cargill Dow under the designation EcoPLA.

Suitable thermoplastic polyurethane polymers for use in the inventionare commercially available from The Dow Chemical Company under thedesignation PELLATHANE.

Suitable polyolefin carbon monoxide interpolymers can be manufacturedusing well known high pressure free-radical polymerization methods.However, they may also be manufactured with the use of so-calledhomogeneous catalyst systems such as those described and referencedabove.

Suitable free-radical initiated high pressure carbonyl-containingethylene polymers such as ethylene acrylic acid interpolymers can bemanufactured by any technique known in the art including the methodstaught by Thomson and Waples in U.S. Pat. Nos. 3,520,861, 4,988,781;4,599,392 and 5,384,373.

Suitable ethylene vinyl acetate interpolymers for use in the inventionare commercially available from various suppliers, including ExxonChemical Company and Du Pont Chemical Company.

Suitable ethylene/alkyl acrylate interpolymers are commerciallyavailable from various suppliers. Suitable ethylene/acrylic acidinterpolymers are commercially available from The Dow Chemical Companyunder the designation PRIMACOR. Suitable ethylene/methacrylic acidinterpolymers are commercially available from Du Pont Chemical Companyunder the designation NUCREL.

Chlorinated polyethylene (CPE), especially chlorinated substantiallylinear ethylene polymers, can be prepared by chlorinating polyethylenein accordance with well known techniques. Preferably, chlorinatedpolyethylene comprises equal to or greater than 30 weight percentchlorine. Suitable chlorinated polyethylenes for use in the inventionare commercially supplied by The Dow Chemical Company under thedesignation TYRIN.

The polypropylene polymer, if elastic, can also be shaped or fabricatedinto elastic films, coatings, sheets, strips, tapes, ribbons and thelike. The elastic film, coating and sheet of the present invention maybe fabricated by any method known in the art, including blown bubbleprocesses (e.g., simple bubble as well as biaxial orientation techniquessuch trapped bubble, double bubble and tenter framing), cast extrusion,injection molding processes, thermoforming processes, extrusion coatingprocesses, profile extrusion, and sheet extrusion processes. Simpleblown bubble film processes are described, for example, in TheEncyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, JohnWiley & Sons, New York, 1981, Vol. 16, pp. 416–417 and Vol. 18, pp.191–192. The cast extrusion method is described, for example, in ModernPlastics Mid-October 1989 Encyclopedia Issue, Volume 66, Number 11,pages 256 to 257. Injection molding, thermoforming, extrusion coating,profile extrusion, and sheet extrusion processes are described, forexample, in Plastics Materials and Processes, Seymour S. Schwartz andSidney H. Goodman, Van Nostrand Reinhold Company, New York, 1982, pp.527–563, pp. 632–647, and pp. 596–602.

Not only can the polymers of this invention be blended with one or moreother polymers, but they can also be blended with various additives suchas nucleating, clarifying, stiffness and/or crystallization rate agents.These agents are used in a conventional matter and in conventionalamounts.

The polymers of this invention can also be functionalized by adding oneor more functional groups, e.g. through the use of a functionalizedazide, to the polymer chain in a post-reaction operation. Optionally,the polymers of this invention can be subjected to post-reactiontreatments, e.g. crosslinking, vis-breaking, and the like. Vis-breakingis particularly useful in reducing the viscosity of high molecularweight polymers. These post treatments are also used in theirconventional manner.

The following examples are given to illustrate various embodiments ofthe invention. They do not intend to limit the invention as otherwisedescribed and claimed herein. All numerical values are approximate. Whena numerical range is given, it should be understood that embodimentsoutside the range are still within the scope of the invention unlessotherwise indicated. In the following examples, various polymers werecharacterized by a number of methods. Performance data of these polymerswere also obtained. Most of the methods or tests were performed inaccordance with an ASTM standard, if applicable, or known procedures.All parts and percentages are by weight unless otherwise indicated.FIGS. 21A and 21B illustrate the chemical structures of variouscatalysts described in the following examples.

Specific Embodiments

Tetrahydrofuran (THF), diethyl ether, toluene, hexane, and ISOPAR E(obtainable from Exxon Chemicals) are used following purging with pure,dry nitrogen and passage through double columns charged with activatedalumina and alumina supported mixed metal oxide catalyst (Q-5 catalyst,available from Engelhard Corp). All syntheses and handling of catalystcomponents are performed using rigorously dried and deoxygenatedsolvents under inert atmospheres of nitrogen or argon, using eitherglove box, high vacuum, or Schlenk techniques, unless otherwise noted.MMAO-3A, PMAO, and PMAO-IP can be purchased from Akzo-Nobel Corporation.

Synthesis of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) (Catalyst A)

Catalyst A can be synthesized according to Example 17 of U.S. Pat. No.5,556,928.

Synthesis of dimethylsilyl(2-methyl-s-indacenyl)(t-butylamido) titanium1,3-pentadiene (Catalyst B)

Catalyst B can be synthesized according to Example 23 of U.S. Pat. No.5,965,756.

Synthesis of(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium(Catalyst C) (1) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di(p-tolyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium

(A) Preparation ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine:

To a 1.70 g (5.35 mmol) ofN-(tert-butyl)-N-(1-chloro-1,1-di(3-p-tolyl)silylamine dissolved in 20mL of THF is added 1.279 g (5.35 mmol) of1-(1H-3-indenyl)-1-(2,3-dihydro-1H-isoindolinyl) lithium salt dissolvedin 20 mL of THF. After the addition, the reaction mixture is stirred for9 hours and then solvent is removed under reduced pressure. The residueis extracted with 40 mL of hexane and filtered. Solvent is removed underreduced pressure giving 2.806 of product as a gray solid.

¹H (C₆D₆) δ: 1.10 (s, 9H), 2.01 (s, 3H), 2.08 (s, 3H), 4.12 (d, 1H,³J_(H-H)=1.5 Hz), 4.39 (d, 1H, ²J_(H-H)=11.1 Hz), 4.57 (d, 1H,²J_(H-H)=11.7 Hz), 5.55 (d, 1H, ³J_(H-H)=2.1 Hz), 6.9–7.22 (m, 10H),7.56 (d, 1H, ³J_(H-H)=7.8 Hz), 7.62 (d, 1H, ³J_(H-H)=6.9 Hz), 7.67 (d,1H, ³J_(H-H)=7.8 Hz), 7.83 (d, 1H, ³J_(H-H)=7.8 Hz).

¹³C{¹H} (C₆D₆) δ: 21.37, 21.43, 33.78, 41.09, 50.05, 56.56, 104.28,120.98, 122.46, 123.84, 124.71, 124.84, 126.98, 128.29, 128.52, 129.05,132.99, 133.68, 135.08, 135.90, 136.01, 138.89, 139.05, 139.09, 141.27,146.39, 148.48.

(B) Preparation ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine,dilithium salt:

To a 50 mL hexane solution containing 2.726 g (5.61 mmol) of theN-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amineis added 7.4 mL of 1.6 M n-BuLi solution. During addition of the n-BuLi,a yellow precipitate appears. After stirring for 6 hours, the yellowprecipitate is collected on a frit, washed with 2×25 mL of hexane, anddried under reduced pressure to give 2.262 g of the product as a yellowpowder.

¹H(C₆D₆) δ: 1.17 (s, 9H), 2.30 (s, 6H), 4.51 (s, 4H), 6.21 (s, 1H), 6.47(m, 2H), 6.97 (d, 4H, ³J_(H-H)=8.1 Hz), 7.15 (m, 2H), 7.23 (m, 2H), 7.50(m, 1H), 7.81 (d, 4H, ³J_(H-H)=7.8 Hz), 8.07 (d, 1H, ³J_(H-H)=7.2 Hz).¹³C{¹H} (C₆D₆) δ: 21.65, 38.83, 52.46, 59.82, 95.33, 112.93, 114.15,115.78, 118.29, 122.05, 122.60, 124.16, 124.78, 126.94, 127.30, 133.06,134.75, 137.30, 141.98, 148.17.

(C) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium:

In the drybox 1.552 g (4.19 mmol) of TiCl₃(THF)₃ is suspended in 20 mLof THF. To this solution, 2.206 g (4.19 mmol) ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine,dilithium salt dissolved in 30 mL of THF is added within 1 minute. Thesolution is then stirred for 60 minutes. After this time, 0.76 g ofPbCl₂ (2.75 mmol) is added and the solution is stirred for 60 minutes.The THF is then removed under reduced pressure. The residue is firstextracted with 60 mL of methylene chloride and filtered. Solvent isremoved under reduced pressure leaving a black crystalline solid. Hexaneis added (30 mL) and the black suspension is stirred for 10 hour. Thesolids are collected on a frit, washed with 30 mL of hexane and driedunder reduced pressure to give 2.23 g of the desired product as a deeppurple solid.

¹H (THF-d₈) δ: 1.40 (s, 9H), 2.46 (s, 3H), 2.48 (s, 3H), 5.07 (d, 2H,²J_(H-H)=12.3 Hz), 5.45 (d, 2H, ²J_(H-H)=12.6 Hz), 5.93 (s, 1H), 6.95(d, 1H, ³J_(H-H)=9.0 Hz), 7.08 (d, 1H, ³J_(H-H)=7.8 Hz), 7.15–7.4 (m,9H), 7.76 (d, 1H, ³J_(H-H)=7.8 Hz), 7.82 (d, 1H, ³J_(H-H)=7.5 Hz), 8.05(d, 1H, ³J_(H-H)=8.7 Hz). ¹³C{¹H} (THF-d₈) δ: 21.71, 21.76, 33.38,56.87, 61.41, 94.5, 107.95, 122.86, 125.77, 126.68, 127.84, 127.92,128.40, 128.49, 129.36, 129.79, 131.23, 131.29, 135.79, 136.43, 136.73,141.02, 141.22, 150.14.

(2) Preparation of(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium:

In the drybox 0.50 g ofdichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titaniumcomplex (0.79 mmol) is dissolved in 30 mL of diethyl ether. To thissolution, 1.14 mL (1.6 mmol) of MeLi (1.6 M in ether) is added dropwisewhile stirring over a 1 minute period. After the addition of MeLi iscompleted, the solution is stirred for 1.5 hour. Diethyl ether isremoved under reduced pressure and the residue extracted with 45 mL ofhexane. Hexane is removed under reduced pressure giving a redcrystalline material. This solid is dissolved in about 7 mL of tolueneand 25 mL of hexane, filtered, and the solution was put into the freezer(−27° C.) for 2 days. The solvent is then decanted and the resultingcrystals are washed with cold hexane and dried under reduced pressure togive 156 mg of product.

¹H (C₆D₆) δ: 0.25 (s, 3H), 0.99 (3H), 1.72 (s, 9H), 2.12 (s, 3H), 2.15(s, 3H), 4.53 (d, 2H, ²J_(H-H)=11.7 Hz), 4.83 (d, 2H, ²J_(H-H)=11.7 Hz),5.68 (s, 1H), 6.72 (dd, 1H, ³J_(H-H)=8.6 Hz, ³J_(H-H)=6.6 Hz), 6.9–7.2(m, 11H), 7.30 (d, 1H, ³J_(H-H)=8.6 Hz),7.71 (d, 1H, ³J_(H-H)=8.5 Hz),7.93 (d, 1H, ³J_(H-H)=7.8 Hz), 8.11 (d, 1H, ³J_(H-H)=7.8 Hz). ¹³C{¹H}(C₆D₆) δ: 21.45, 21.52, 35.30, 50.83, 56.03, 56.66, 57.65, 83.80,105.64, 122.69, 124.51, 124.56, 125.06, 125.35, 127.33, 128.98, 129.06,129.22, 133.51, 134.02, 134.62, 136.49, 136.84, 137.69, 139.72, 139.87,143.84.

Synthesis of (1H-cyclopenta [1]phenanthrene-2-yl)dimethyl(t-butylamido)silane titanium dimethyl(Catalyst D)

Catalyst D can be synthesized according to Example 2 of U.S. Pat. No.6,150,297.

Synthesis ofrac-[dimethylsilylbis(1-(2-methyl-4-phenyl)indenyl)]zirconium(1,4-diphenyl-1,3-butadiene) (Catalyst E)

Catalyst E can be synthesized according to Example 15 of U.S. Pat. No.5,616,664.

Synthesis of rac-[1,2-ethanediylbis(1-indenyl)]zirconium(1,4-diphenyl-1,3-butadiene) (Catalyst Catalyst F can be synthesizedaccording to Example 11 of U.S. Pat. No. 5,616,664. Synthesis ofCatalyst G

Hafnium tetrakisdimethylamine. The reaction is prepared inside of a drybox. A 500 mL round bottom flask containing a stir bar, is charged with200 mL of toluene and LiNMe₂ (21 g, 95%, 0.39 mol). HfCl₄ (29.9 g, 0.093mol) is added slowly over 2 h. The temperature reaches 55° C. Themixture is stirred overnight at ambient temperature. The LiCl isfiltered off. The toluene is carefully distilled away from the product.Final purification is achieved by distillation with a vacuum transferline attached to a cold (−78° C.) receiving flask. This process isperformed outside the dry box on a Schlenk line. The material isdistilled over at 110–120° C. at 300–600 microns. The 19.2 g of thewhite solid is collected.

2-formyl-6-naphthylpyridine. Inside of a dry box, naphthylboronic acid(9.12 g, 53.0 mmol) and Na₂CO₃ (11.64 g, 110 mmol) are dissolved in 290mL of degassed 4:1 H₂O/MeOH. This solution is added to a solution of 8 g(43 mmol) of 2-bromo-6-formylpyridine and 810 mg (0.7 mmol) of Pd(PPh₃)₄in 290 mL of degassed toluene. The charged reactor is removed from thedry box, while under a blanket of N₂ and is connected to the house N₂line. The biphasic solution is vigorously stirred and heated to 70° C.for 4 h. On cooling to RT, the organic phase is separated. The aqueouslayer is washed with 3×75 mL of Et₂O. The combined organic extracts arewashed with 3×100 mL of H₂O and 1×100 mL of brine and dried over Na₂SO₄.After removing the volatiles in vacuo, the resultant light yellow oil ispurified via trituration with hexanes. The isolated material isrecrystallized from a hot hexane solution and ultimately yielded 8.75 g,87% yield. mp 65–66° C.

¹H NMR (CDCl₃) δ 7.2–8.3 (m, 10H), 10.25 (s, 1H) ppm. ¹³C NMR (CDCl₃)120.3, 125.64, 125.8, 126.6, 127.26, 128.23, 129.00, 129.74, 130.00,131.39, 134.42, 137.67, 137.97, 153.07, 160.33, 194.23 ppm.6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine: A dry, 500 mL 3-neckround bottom flask is charged with a solution of 5.57 g (23.9 mmol) of2-formyl-6-naphthlypyridine and 4.81 g (27.1 mmol) of2,6-diisopropylaniline in 238 mL of anhydrous THF containing 3 Åmolecular sieves (6 g) and 80 mg of p-TsOH. The loading of the reactoris performed under N₂. The reactor is equipped with a condenser, an overhead mechanical stirrer and a thermocouple well. The mixture is heatedto reflux under N₂ for 12 h. After filtration and removal of thevolatile in vacuo, the crude, brown oil is triturated with hexanes. Theproduct is filtered off and rinsed with cold hexanes. The slightly offwhite solid weighes 6.42 g. No further purification is performed. mp142–144° C.

¹H NMR (CDCl₃) δ 1.3 (d, 12H), 3.14 (m, 2H), 7.26 (m, 3H), 7.5–7.6 (m,5H), 7.75–7.8 (m, 3H), 8.02 (m 1H), 8.48 (m, 2H) ppm. ¹³C NMR (CDCl₃)23.96, 28.5, 119.93, 123.50, 124.93, 125.88, 125.94, 126.49, 127.04,127.24, 128.18, 128.94, 129.7, 131.58, 134.5, 137.56, 137.63, 138.34,148.93, 154.83, 159.66, 163.86 ppm.

(6-naphthyl-2-pyridyl)-N-(2,6-diisopropylphenyl)benzylamine: A 250 mL3-neck flask, equipped with mechanical stirrer and a N₂ sparge, ischarged with 6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (6.19 mg,15.8 mmol) and 80 mL of anhydrous, degassed Et₂O. The solution is cooledto −78° C. while a solution of phenyllithium (13.15 mL of 1.8 M incyclohexane, 23.7 mmol) is added dropwise over 10 min. After warming toRT over 1 h. the solution is stirred at RT for 12 hours. The reaction isthen quenched with ˜50 mL of aq. NH₄Cl. The organic layer is separated,washed with brine and H₂O, then dried over Na₂SO₄. Using the BiotageChromatography system (column # FKO-1107–19073, 5% THF/95% hexanes), theproduct is isolated as a colorless oil. The chromatography is performedby dissolving the crude oil in 50 mL of hexanes. The purification isperformed in 2×˜25 mL batches, using half of the hexane stock solutionfor each run. 7.0 g of the oil is isolated (93% yield).

¹H NMR (CDCl₃) δ 0.90 (d, 12H), 3.0 (m, 2H), 4.86 (s, 1H), 5.16 (s, 1H),7.00 (m, 3H), 7.1–7.6 (m, 12H), 7.8–7.88 (m, 2H), 7.91–7.99 (d, 1H) ppm.¹³C NMR (CDCl₃) 24.58, 28.30, 70.02, 121.14, 123.62, 123.76, 123.95,125.71, 126.32, 126.55, 126.74, 127.45, 128.04, 128.74, 129.47, 131.66,134.49, 137.4, 138.95, 142.68, 143.02, 143.89, 159.36, 162.22 ppm.

Catalyst G-(Nme₂)₃: The reaction is performed inside of a dry box. A 100mL round bottom flask is charged with Hf(Nme₂)₄ (2.5 g, 5.33 mmol), 30mL of pentane and a stir bar. The amine 1 is dissolve in 40 mL ofpentane then added to the stirring solution of Hf(Nme₂)₄. The mixture isstirred at ambient temperature for 16 h (overnight). The light yellowsolid is filtered off and rinsed with cold pentane. The dry weight ofthe powder is 2.45 g. A second crop is collected from the filtrateweighing 0.63 g. The overall yield is 74%.

¹H NMR (C₆D₆) δ 0.39 (d, 3H, J=6.77 Hz), 1.36 (d, 3H, J=6.9 Hz), 1.65(d, 3H, J=6.68 Hz), 1.76 (d, 3H, J=6.78 Hz), 2.34 (br s, 6H), 2.80 (brs, 6H), 2.95 (br s, 6H), 3.42 (m, 1H, J=6.8 Hz), 3.78 (m, 1H, J=6.78Hz), 6.06 (s, 1H), 6.78 (m, 2H), 6.94 (m, 1H), 7.1–7.4 (m, 13H), 7.8 (m,2H) ppm.

Catalyst G: The reaction is performed inside of a dry box. A 100 mLround bottom flask is charged with 70 mL of pentane and 15 mL of a 2.0 Mtrimethyl aluminum in hexane solution. The solution is cooled to −40° C.The hafnium trisamide compound from the previous reaction (1.07 g 1.28mmol) is added in small portions over 5–10 minutes. Upon the addition, awhite gelatinous residue forms. After 45–60 min the reaction becomesyellow with a fine, yellow, powder precipitating from the mixture. Aftera total reaction time of 2.5 h the mixture is filtered and 615 mg ofCatalyst G is isolated as a bright, yellow powder. No furtherpurification is performed.

¹H NMR (C₆D₆) δ 0.51 (d, 3H, J=6.73 Hz), 0.79 (s, 3H), 1.07 (s, 3H),1.28 (d, 3H, J=6.73 Hz), 1.53 (m, 6H), 3.37 (m, 1H, J=6.75 Hz), 3.96 (m,1H, J=6.73 Hz), 6.05 (s, 1H), 6.50 (d, 1H, J=7,75 Hz), 6.92 (t, 1H,J=7.93 Hz), 7.1–7.59 (m, 12H), 7.6 (d, 1H), 7.8–8.0 (m, 2H), 8.3 (m,1H), 8.69 (d, 1H, J=7.65 Hz) ppm.

Synthesis of Catalyst H

To a solution of 9-bromophenanthrene (10.36 mg, 41 mmol) in 132 mL ofanhydrous, degassed Et₂O cooled to −40° C. is added under N₂ 27 mL (43.2mmol) of a 1.6 M solution of n-BuLi in hexanes. The solution is swirledto mix and allowed to react at −40° C. for 3 hours during whichcolorless crystals precipitated from solution. The9-phenanthrenyllithium is added as a slurry to a well-mixed solution of6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (10.6 g, 27.04 mmol)in 130 mL of Et₂O cooled to −40° C. After warming to ambient temperatureover 1 h, the solution is stirred at ambient temperature for 2 hours.The reaction is then quenched with aq. NH₄Cl, and subjected to anaqueous/organic work-up. The organic washes are combined and dried overNa₂SO₄. Upon removal of the volatiles with rotary evaporation, theproduct precipitates from solution. The isolated solids are rinsed withcold hexanes. The material is vacuum dried at 70° C. using the housevacuum over night. The dried material is isolated as a white solid,weighing 12.3 g for a yield of 80%. A second crop is isolated weighing0.37 g. Mp 166–168° C.

¹H NMR (C₆D₆) δ 1.08 (dd, 12H), 3.43 (m, 2H), 5.47 (m, 1H), 6.16 (d,1H), 7.0–7.8 (m, 14H), 8.2 (d, 1H), 8.5–8.6 (m, 4H), ppm. ¹³C NMR(CDCl₃) 24.68, 28.22, 68.87, 120.56, 122.89, 123.63, 123.73, 124.07,124.1, 125.5, 125.59, 126.24, 126.42, 126.52, 126.76, 126.83, 126.9,127.05, 127.14, 128.0, 128.55, 129.49, 129.55, 130.67, 130.71, 131.52,131.55, 132.24, 134.39, 137.57, 143.31, 159.1, 162 ppm.

Catalyst H-(Nme₂)₃: Inside of a dry box, six different teflon-screwcapped, glass pressure tube reactors are each charged with Hf(Nme₂)₄(1.55 g, 4.37 mmol, overall 9.3 g, 26.2 mmol), 10 mL of toluene and theligand isolated from the previous procedure above (2.1 g, 3.68 mmol,overall 12.6 g, 22.1 mmol). The tightly sealed reactors are removed fromthe dry box and placed in a heater block with the temperature set at125° C. The reactor tubes are heated overnight (˜16 h). The cooled tubesare taken into the dry box and the contents of the reactor tubes arecombined in a 500 mL round bottom flask. The flask is placed undervacuum to remove the dimethylamine and toluene. The light yellow/greensolid which is left is rinsed with ˜125 mL of cold pentane and filtered,yielding 13.6 g of a light yellow powder for a yield of 65%.

Catalyst H: The reaction is performed inside of a dry box. A 500 mL jaris charged with 250 mL of pentane and the hafnium amide isolated in theprocedure outlined immediately above (13.6 g, 15.5 mmol). The mixture iscooled to −40° C. To the stirring mixture is slowly added 70 mL of a 2.0M trimethyl aluminum (140 mmol) in hexane solution. After 3 h thereaction becomes yellow with a fine, powder precipitating from themixture. The mixture is then cooled to −40° C. and filtered. Theinitially collected product is rinsed with 2×60 mL of cold pentane.10.24 g Catalyst H is isolated (84% yield) with a purity of >99% by ¹HNMR.

Synthesis of Armeenium Borate[methylbis(hydrogenatedtallowalkyl)ammonium tetrakis (pentafluorophenyl)borate]

Armeenium borate can be prepared from ARMEEN® M2HT (available fromAkzo-Nobel), HCl, and Li [B(C₆F₅)₄] according to Example 2 of U.S. Pat.No. 5,919,983.

General 1 Gallon Continuous Solution Propylene/Ethylene CopolymerizationProcedure

Purified toluene solvent, ethylene, hydrogen, and propylene are suppliedto a 1 gallon reactor equipped with a jacket for temperature control andan internal thermocouple. The solvent feed to the reactor is measured bya mass-flow controller. A variable speed diaphragm pump controls thesolvent flow rate and increases the solvent pressure to the reactor. Thepropylene feed is measured by a mass flow meter and the flow iscontrolled by a variable speed diaphragm pump. At the discharge of thepump, a side stream is taken to provide flush flows for the catalystinjection line and the reactor agitator. The remaining solvent iscombined with ethylene and hydrogen and delivered to the reactor. Theethylene stream is measured with a mass flow meter and controlled with aResearch Control valve. A mass flow controller is used to deliverhydrogen into the ethylene stream at the outlet of the ethylene controlvalve. The temperature of the solvent/monomer is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters, and are combined with the catalystflush solvent. This stream enters the bottom of the reactor, but in adifferent port than the monomer stream. The reactor is run liquid-fullat 500 psig with vigorous stirring. The process flow is in from thebottom and out of the top. All exit lines from the reactor are steamtraced and insulated. Polymerization is stopped with the addition of asmall amount of water, and other additives and stabilizers can be addedat this point. The stream flows through a static mixer and a heatexchanger in order to heat the solvent/polymer mixture. The solvent andunreacted monomers are removed at reduced pressure, and the product isrecovered by extrusion using a devolatilizing extruder. The extrudedstrand is cooled under water and chopped into pellets. The operation ofthe reactor is controlled with a process control computer.

EXAMPLE 1 Propylene/Ethylene Polymerization Using Metallocene Catalyst E(Comparative)

The general procedure for the 1 gallon continuous solutionpolymerization outlined above was employed. A catalyst solutioncontaining 2.6 ppm Zr from Catalyst E was prepared and added to a 4 Lcatalyst storage tank. This solution was combined in a continuous streamwith a continuous stream of a solution containing Armeeniumtetrakis(pentafluorophenyl)borate in toluene and a continuous stream ofa solution of PMAO-IP in toluene to give a ratio of total Ti:B:Al of1:1.2:30. The activated catalyst solution was fed continuously into thereactor at a rate sufficient to maintain the reactor temperature atapproximately 80° C. and a polymer production rate of approximately 3pounds an hour. The polymer solution was continuously removed from thereactor exit and was contacted with a solution containing 100 ppm ofwater for each part of the polymer solution, and polymer stabilizers(i.e., 1000 ppm Irgaphos 168 and 1000 ppm Irganox 1010 per part of thepolymer). The resulting exit stream was mixed, heated in a heatexchanger, and the mixture was introduced into a separator where themolten polymer was separated from the solvent and unreacted monomers.The resulting molten polymer was extruded and chopped into pellets afterbeing cooled in a water bath. For this example, the propylene toethylene ratio was 22.0. Product samples were collected over 1 hour timeperiods, after which time the melt flow rate was determined for eachsample. FIG. 9 is a ¹³C NMR of Comparative Example 1, and itdemonstrates the absence of regio-error peaks in the region around 15ppm.

EXAMPLES 2–6

Examples 2–6 were conducted similar to Example 1 except as otherwisenoted in Tables 2-6-1 and 2-6-2 below. Catalyst E is listed forcomparative purposes. FIG. 8 is the ¹³C NMR sprectrum of thepropylene/ethylene copolymer product of Example 2. FIGS. 2A and 2B showa comparison of the DSC heating traces of the propylene/ethylenecopolymers of Comparative Example 1 and Example 2.

TABLE 2-6-1 Polymerization Conditions POLY Reactor SOLV C2 C3 H2 LBS/HRTEMP FLOW FLOW FLOW FLOW production Example DEGC LB/HR LB/HR LB/HR SCCMrate 1 80.5 36.0 0.50 11.00 0 3.13 (compar- ative) 2 80.5 33.0 0.20 6.0020.8 3.47 3 80.1 26.0 0.10 6.00 14.1 3.09 4 79.9 26.0 0.20 6.00 20.13.25 5 80.0 26.0 0.30 6.00 26.1 3.16 6 80.3 26.0 0.40 6.00 32.1 3.32

TABLE 2-6-2 Monomer conversion and activity catalyst efficiency C3/C2propylene ethylene concentration g metal Example Catalyst ratioconversion conversion ppm(metal) per g polymer 1 E 22.00 25.7% 64.8% 2.66,145,944 (comparative) 2 G 30.17 53.1% 99.1% 25.6 235,823 3 H 61.0748.7% 98.4% 55.0 225,666 4 H 30.34 49.7% 99.0% 55.0 259,545 5 H 20.1746.8% 98.6% 55.0 259,282 6 H 15.00 48.0% 98.7% 55.0 278,579

TABLE 2-6-3 Summary of Polymer Analysis Data DSC MFR Density Cryst. (%)Tg Tc,o Tc,p Example (g/10 min) (kg/dm3) from density (° C.) (° C.) (°C.) 1 72 0.8809 37.9 −26.1 52.3 47.6 2 1.7 0.8740 29.6 −24.8 59.0 49.3 32.2 0.8850 42.8 −10.0 76.6 64.5 4 2.3 0.8741 29.7 −23.2 50.8 41.6 5 20.8648 18.3 −27.1 30.4 10.9 6 2.0 0.8581 9.9 −29.6 — —

TABLE 2-6-4 Summary of Polymer Analysis Data cont'd ΔHc Cryst. (%) Tm,pTm,e ΔHf Cryst. (%) Example (J/g) (from Hc) (° C.) (° C.) (J/g) (fromHf) 1 40.8 24.7 91.9 114.3 52.1 31.6 2 27.1 16.4 64.5 128.9 38.0 23.0 345.0 27.3 102.2 145.7 65.3 39.6 4 30.6 18.5 67.4 145.6 42.9 26.0 5 8.75.3 50.0 119.4 13.0 7.9 6 — — — — — —

TABLE 2-6-5 Summary of Polymer Analysis Data cont'd Ethylene EthyleneRegio-errors Mn Mw Example (wt %)* (mol %)* 14–16 ppm(mol %)* (kg/mol)(kg/mol) MWD 1 9.5 13.6 0.00 58.5 117.4 2.0 2 8.2 11.8 0.24 132.6 315.72.4 3 5.6 8.2 0.46 146.0 318.3 2.2 4 8.2 11.8 0.34 138.5 305.7 2.2 511.1 15.8 0.35 6 13.2 18.6 0.37 127.5 306.8 2.4 *determined by NMR

TABLE 2-6-6 Summary of Polmer Analysis Data cont'd Example % mm* % mr* %rr* 1 98.55 0 1.45 2 93.28 1.09 5.68 3 94.3 2.21 3.43 4 96.37 0 3.63 595.3 0.0 4.66 6 95.17 0 4.83 *corrected PPE + EPE

EXAMPLES 7–8 Homopolymerization of Propylene Using Catalyst B and C

Examples 7–8 were conducted similar to Example 1 without ethylene. Theprocedure was similar to Example 1 with exceptions noted in Tables 7-8-1and 7-8-2 below. FIG. 6 shows the ¹³C NMR spectrum of the propylenehomopolymer product of Example 7 prepared using catalyst G. FIG. 7 showsthe ¹³C NMR spectrum of the propylene homopolymer product of Example 8prepared using catalyst H. Both spectra show a high degree ofisotacticity, and the expanded Y-axis scale of FIG. 7 relative to FIG. 6shows more clearly the regio-error peaks. FIGS. 23A and 23B show the DSCheating and cooling traces of the propylene homopolymer of Example 8.

TABLE 7-8-1 Reactor Conditions and Catalyst Activity Reactor SOLV C3 H2POLY catalyst efficiency TEMP FLOW FLOW FLOW LBS/HR propyleneconcentration g metal Example DEGC LB/HR LB/HR SCCM WEIGHED Catalystconversion ppm(metal) per g polymer 7 99.8 33.1 6.00 1.9 2.30 G 38.3%25.6 111,607 8 100.3 26.0 6.00 2.6 2.57 H 42.8% 32.5 100,987

TABLE 7-8-2 Polymer Analysis DSC MFR Density Cryst. (%) Tg Tc,o Tc,p MnMw Example (g/10 min) (kg/dm3) from density (° C.) (° C.) (° C.)(kg/mol) (kg/mol) MWD 7 1.9 0.8995 59.7 −6.0 104.2 100.4 114.6 350.8 2.78 2.5 0.9021 62.7 −8.1 105.7 103.3 125.5 334.0 2.7

TABLE 7-8-3 Polymer Analysis Continued ΔHc Cryst. (%) Tm,p Tm,e ΔHfCryst. (%) Regio-errors Example (J/g) (from Hc) (° C.) (° C.) (J/g)(from Hf) 14–16 ppm(mol %)* % mm % mr % rr 7 76.9 46.6 139.7 153.5 93.756.8 2.69 92.12 5.79 2.08 8 83.6 50.7 144.5 158.2 100.6 61.0 2.36 93.934.45 1.62 *determined by NMR

EXAMPLE 9

This Example demonstrates a series dual-reactor continuous solutionprocess with the use of a hafnium pyridyl amine catalyst (Catalyst H) inthe first reactor to produce high molecular weight isotacticpolypropylene and a constrained geometry catalyst (Catalyst B) in thesecond reactor to produce a lower molecular weight atacticpropylene/ethylene copolymer, and recovery of the novel polymer.

Purified ISOPAR-E solvent, ethylene, hydrogen, and 1-octene are suppliedto a 1-gallon jacketed reactor equipped with a jacket for temperaturecontrol and an internal thermocouple. The solvent feed to the reactor ismeasured by a mass-flow controller. A variable speed diaphragm pumpcontrols the solvent flow rate and increases the solvent pressure to thereactor. The compressed, liquified propylene feed is measured by a massflow meter and the flow is controlled by a variable speed diaphragmpump. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst injection line and the reactor agitator.The remaining solvent is combined with ethylene and hydrogen anddelivered to the reactor. The ethylene stream is measured with a massflow meter and controlled with a Research Control valve. A mass flowcontroller is used to deliver hydrogen into the ethylene stream at theoutlet of the ethylene control valve. The temperature of thesolvent/monomer is controlled by use of a heat exchanger before enteringthe reactor. This stream enters the bottom of the reactor. The catalystcomponent solutions are metered using pumps and mass flow meters, andare combined with the catalyst flush solvent. This stream enters thebottom of the reactor, but in a different port than the monomer stream.The reactor is run liquid-full at 500 psig with vigorous stirring. Theprocess flow is in from the bottom and out of the top. All exit linesfrom the reactor are steam traced and insulated. The exit of the firstreactor is connected by insulated piping to a second 1 gallon reactorsimilarly equipped to the first, with a provision for independentcatalyst and cocatalyst addition, and additional monomer, hydrogen,solvent addition and jacket temperature control. After the polymersolution stream exits the second reactor, polymerization is stopped withthe addition of a small amount of water, and other additives andstabilizers can be added at this point. The stream flows through astatic mixer and a heat exchanger in order to heat the solvent/polymermixture. The solvent and unreacted monomers are removed at reducedpressure, and the product is recovered by extrusion using adevolatilizing extruder. The extruded strand is cooled under water andchopped into pellets. The operation of the dual-reactor system iscontrolled with a process control computer.

A 4-L catalyst tank is filled with an ISOPAR E solution of Catalyst H ata concentration of 50 ppm Hf. A second 4 L catalyst tank is filled witha solution of Catalyst B at a concentration of 5.0 ppm Ti. Additionaltanks are provided with a solution of N,N-dioctadecylaniliniumtetrakis(pentafluorophenyl)borate in ISOPAR E at a concentration of 100ppm B, and MMAO-3A in ISOPAR E at a concentration of 100 ppm Al. ISOPARE is continuously fed into the first reactor at 27.0 pounds per hour,and propylene at 6.0 pounds per hour. The Catalyst H solution, alongwith enough N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)boratein ISOPAR E and MMAO-3A in ISOPAR E to maintain a Hf:B:Al molar ratio of1:1.2:5 is added to the first reactor at a rate sufficient to maintain a55% propylene conversion and a reaction temperature of 100° C. The flowrate of Catalyst H is adjusted to maintain a first-reactor product meltflow rate (MFR) of 2.0, while maintaining 55% propylene conversion and areactor temperature of 100° C. by adjusting the temperature of thereactor jacket and through the addition of hydrogen as a molecularweight control agent. The molar ratio of aluminum can be adjusted inorder to optimize the overall catalyst efficiency. The contents of thefirst reactor flow into the second reactor, where additional solvent (10pounds/hr) and a mixture of propylene and ethylene (2.0 and 1.0pounds/hour, respectively) is added at 20° C. The Catalyst B solution,along with enough N,N-dioctadecylaniliniumtetrakis(pentafluorophenyl)borate in ISOPAR E and MMAO-3A in ISOPAR E tomaintain a Ti:B:Al molar ratio of 1:1.2:5 is added to the second reactorat a rate sufficient to maintain a 80% ethylene conversion and areaction temperature of 120° C. The flow rate of Catalyst B is adjustedto maintain an overall product melt flow rate (MFR) of 6.0 by adjustingthe temperature of the reactor jacket and through the addition ofhydrogen as a molecular weight control agent. The molar ratio ofaluminum can be adjusted in order to optimize the overall catalystefficiency. After the post-reactor deactivation of the catalyst,antioxidant is added, and the product is devolatilized and extruded torecover the solid product, which is useful for molding and extrusion,and has good processability and toughness.

EXAMPLE 10

This Example demonstrates a series dual-reactor continuous solutionprocess with the use of a hafnium pyridyl amine catalyst (Catalyst H) inthe first reactor to produce high molecular weight isotacticpropylene/ethylene copolymer and a metallocene catalyst (Catalyst E) inthe second reactor to produce a lower molecular weight isotacticpolypropylene, and recovery of the novel polymer. This exampledemonstrates a high conversion of ethylene in the first reactor, whichallows for a more crystalline product to be made in the second reactor.

The procedure of Example 9 is followed except that Catalyst H is addedto the first reactor along with 26 pounds/hr of toluene, 6.0 pounds/hrof propylene, and 0.2 pounds/hr of ethylene. The Catalyst H solution,along with enough N,N-dioctadecylaniliniumtetrakis(pentafluorophenyl)borate in toluene and PMAO-IP in TOLUENE tomaintain a Hf:B:Al molar ratio of 1:1.2:30 is added to the first reactorat a rate sufficient to maintain a 52% propylene conversion and areaction temperature of 80° C. The flow rate of Catalyst H is adjustedto maintain a first-reactor product melt flow rate (MFR) of 0.2, whilemaintaining 52% propylene conversion and a reactor temperature of 80° C.by adjusting the temperature of the reactor jacket and through theaddition of hydrogen as a molecular weight control agent. At thispropylene conversion, the ethylene conversion is about 99%. The molarratio of aluminum can be adjusted in order to optimize the overallcatalyst efficiency. The contents of the first reactor flow into thesecond reactor, where additional solvent (20 pounds/hr) and propylene(2.0 pounds/hr) is added at 20° C. The Catalyst E solution, along withenough N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate inISOPAR E and MMAO-3A in ISOPAR E to maintain a Zr:B:Al molar ratio of1:1.2:5 is added to the second reactor at a rate sufficient to maintainthe reactor temperature at 100° C. The flow rate of Catalyst E isadjusted to maintain the temperature at 100° C. and an overall productmelt flow rate (MFR) of 20 by adjusting the temperature of the reactorjacket and through the addition of hydrogen as a molecular weightcontrol agent as needed. The molar ratio of aluminum can be adjusted inorder to optimize the overall catalyst efficiency. After thepost-reactor deactivation of the catalyst, antioxidant is added, and theproduct is devolatilized and extruded to recover the novel solidproduct, which has a broad molecular weight distribution, and has goodprocessability and toughness.

EXAMPLE 11

This Example demonstrates a series dual-reactor continuous solutionprocess with the use of a hafnium pyridyl amine catalyst (Catalyst H) inthe first reactor to produce high molecular weight isotacticpolypropylene and a metallocene catalyst (Catalyst F) in the secondreactor to produce a lower molecular weight isotactic polypropylenehaving a lower tacticity than the first reactor polymer, and recovery ofthe novel polymer.

The procedure of Example 10 is followed except that Catalyst H is addedto the first reactor along with 26 pounds/hour of toluene, and 7.0pounds/hr of propylene. The Catalyst H solution, along with enoughN,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate in tolueneand PMAO-IP in toluene to maintain a Hf:B:Al molar ratio of 1:1.2:30 isadded to the first reactor at a rate sufficient to maintain a 52%propylene conversion and a reaction temperature of 90° C. The flow rateof Catalyst H is adjusted to maintain a first-reactor product melt flowrate (MFR) of 0.10, while maintaining 52% propylene conversion and areactor temperature of 90° C. by adjusting the temperature of thereactor jacket and through the addition of hydrogen as a molecularweight control agent, as needed. The molar ratio of aluminum can beadjusted in order to optimize the overall catalyst efficiency. Thecontents of the first reactor flow into the second reactor, whereadditional solvent (20 pounds/hr) and propylene (2.0 pounds/hr) is addedat 20° C. The Catalyst F solution, along with enoughN,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate in tolueneand PMAO-IP in toluene to maintain a Zr:B:Al molar ratio of 1:1.2:5 isadded to the second reactor at a rate sufficient to maintain the reactortemperature at 120° C. The flow rate of Catalyst F is adjusted tomaintain the temperature at 120° C. and an overall product melt flowrate (MFR) of 12 by adjusting the temperature of the reactor jacket andthrough the addition of hydrogen as a molecular weight control agent asneeded. The molar ratio of aluminum can be adjusted in order to optimizethe overall catalyst efficiency. After the post-reactor deactivation ofthe catalyst, antioxidant is added, and the product is devolatilized andextruded to recover the novel solid product, which has a very broadmolecular weight distribution, and has good processability and is usefulfor molding applications, among others.

EXAMPLE 12

This Example demonstrates a series dual-reactor continuous solutionprocess with the use of a hafnium pyridyl amine catalyst (Catalyst H) inthe first reactor to produce high molecular weight isotacticpropylene/ethylene copolymer and a constrained geometry catalyst(Catalyst C) in the second reactor to produce a high molecular weightatactic ethylene/propylene copolymer, and recovery of the novel polymer.

The procedure of Example 9 is followed except that Catalyst H is addedto the first reactor along with 26 pounds/hr of ISOPAR-E, 6.0 pounds/hrof propylene, and 0.2 pounds/hr of ethylene. The Catalyst H solution,along with enough N,N-dioctadecylaniliniumtetrakis(pentafluorophenyl)borate in ISOPAR E and MMAO-3A in ISOPAR E tomaintain a Hf:B:Al molar ratio of 1:1.2:5 is added to the first reactorat a rate sufficient to maintain a 55% propylene conversion and areaction temperature of 80° C. The flow rate of Catalyst H is adjustedto maintain a first-reactor product melt flow rate (MFR) of 6.0, whilemaintaining 55% propylene conversion and a reactor temperature of 80° C.by adjusting the temperature of the reactor jacket and through theaddition of hydrogen as a molecular weight control agent. At thispropylene conversion, the ethylene conversion is about 99%. The molarratio of aluminum can be adjusted in order to optimize the overallcatalyst efficiency. The contents of the first reactor flow into thesecond reactor, where additional solvent (22 pounds/hr) and ethylene(3.0 pounds/hr) is added at 20 degrees C. The Catalyst C solution, alongwith enough N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)boratein ISOPAR E and MMAO-3A in ISOPAR E to maintain a Ti:B:Al molar ratio of1:1.2:5 is added to the second reactor at a rate sufficient to maintainthe reactor temperature at 160° C. The flow rate of Catalyst C isadjusted to maintain the temperature at 160° C. and an overall productmelt flow rate (MFR) of 2.0 by adjusting the temperature of the reactorjacket and through the addition of hydrogen as a molecular weightcontrol agent as needed. The molar ratio of aluminum can be adjusted inorder to optimize the overall catalyst efficiency. After thepost-reactor deactivation of the catalyst, antioxidant is added, and theproduct is devolatilized and extruded to recover the novel solidproduct, which has a broad molecular weight distribution, and has goodprocessability and very good toughness.

EXAMPLE 13

This Example demonstrates a series dual-reactor continuous solutionprocess with the use of a hafnium pyridyl amine catalyst (Catalyst H) inthe first reactor to produce high molecular weight isotacticpolypropylene and a constrained geometry catalyst (Catalyst A) in thesecond reactor to produce a lower molecular weight atacticpolypropylene, and recovery of the novel polymer.

The procedure of Example 9 is followed except that Catalyst H is addedto the first reactor along with 26 pounds/hr of ISOPAR-E, and 6.0pounds/hour of propylene. The Catalyst H solution, along with enoughN,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate in ISOPAR Eand MMAO-3A in ISOPAR E to maintain a Hf:B:Al molar ratio of 1:1.2:5 isadded to the first reactor at a rate sufficient to maintain a 50%propylene conversion and a reaction temperature of 90° C. The flow rateof Catalyst H is adjusted to maintain a first-reactor product melt flowrate (MFR) of 0.1, while maintaining 50% propylene conversion and areactor temperature of 90° C. by adjusting the temperature of thereactor jacket and through the addition of hydrogen as a molecularweight control agent. The molar ratio of aluminum can be adjusted inorder to optimize the overall catalyst efficiency. The contents of thefirst reactor flow into the second reactor, where additional solvent (22pounds/hr) and propylene (3.0 pounds/hr) is added at 20° C. The CatalystA solution, along with enough N,N-dioctadecylaniliniumtetrakis(pentafluorophenyl)borate in ISOPAR E and MMAO-3A in ISOPAR E tomaintain a Ti:B:Al molar ratio of 1:1.2:5 is added to the second reactorat a rate sufficient to maintain the reactor temperature at 120° C. Theflow rate of Catalyst C is adjusted to maintain the temperature at 120°C. and an overall product melt flow rate (MFR) of 25 by adjusting thetemperature of the reactor jacket and through the addition of hydrogenas a molecular weight control agent as needed. The molar ratio ofaluminum can be adjusted in order to optimize the overall catalystefficiency. After the post-reactor deactivation of the catalyst,antioxidant is added, and the product is devolatilized and extruded torecover the novel solid product, which has a very broad molecular weightdistribution, and has good processability.

EXAMPLE 14

This Example demonstrates a series dual-reactor continuous solutionprocess with the use of a hafnium pyridyl amine catalyst (Catalyst H) inthe first reactor to produce high molecular weight isotacticpropylene/ethylene copolymer and a constrained geometry catalyst(Catalyst D) in the second reactor to produce a lower molecular weightethylene/styrene/propylene terpolymer, and recovery of the novelpolymer.

The procedure of Example 10 is followed except that Catalyst H is addedto the first reactor along with 26 pounds/hour of toluene, and 6.0pounds/hour of propylene, and 0.3 pounds/hour of ethylene. The CatalystH solution, along with enough N,N-dioctadecylaniliniumtetrakis(pentafluorophenyl)borate in toluene and PMAO-IP in toluene tomaintain a Hf:B:Al molar ratio of 1:1.2:30 is added to the first reactorat a rate sufficient to maintain a 50% propylene conversion and areaction temperature of 80° C. The flow rate of Catalyst H is adjustedto maintain a first-reactor product melt flow rate (MFR) of 0.1, whilemaintaining 50% propylene conversion and a reactor temperature of 80° C.by adjusting the temperature of the reactor jacket and through theaddition of hydrogen as a molecular weight control agent. The molarratio of aluminum can be adjusted in order to optimize the overallcatalyst efficiency. The contents of the first reactor flow into thesecond reactor, where additional solvent (22 pounds/hr) and styrene andethylene (3.0 and 3.5 pounds/hr each, respectively) is added at 20° C.The Catalyst D solution, along with enough N,N-dioctadecylaniliniumtetrakis(pentafluorophenyl)borate in toluene and PMAO-IP in toluene tomaintain a Ti:B:Al molar ratio of 1:1.2:10 is added to the secondreactor at a rate sufficient to maintain the reactor temperature at 120°C. The flow rate of Catalyst D is adjusted to maintain the temperatureat 120° C. and an overall product melt flow rate (MFR) of 3.5 byadjusting the temperature of the reactor jacket and through the additionof hydrogen as a molecular weight control agent as needed. The molarratio of aluminum can be adjusted in order to optimize the overallcatalyst efficiency. After the post-reactor deactivation of thecatalyst, antioxidant is added, and the product is devolatilized andextruded to recover the novel solid product, which is tough and can beused for a variety of molding and extrustion applications, and can beeasily sulfonated with chlorosulfonic acid to produce a novel material,if desired.

EXAMPLE 15

This Example demonstrates a batch reactor polymerization using CatalystH. This example provides a simple and convenient procedure for preparingsmall quantities of the polymers of this invention. Because the peakpositions of ¹³C chemical shifts may vary somewhat from instrument toinstrument depending on the specifics of the solvent, temperature, andother experimental details, this example may be used to prepare a sampleof polymer for the skilled artisan to precisely measure and identify thechemical shifts of the regioerror peaks which are found at about 14.6and 15.7 ppm.

Preparation of Antioxidant/Stabilizer Additive solution: The additivesolution was prepared by dissolving 6.66 g of Irgaphos 168 and 3.33 g ofIrganox 1010 in 500 mL of toluene. The concentration of this solution istherefore 20 mg of total additive per 1 mL of solution.General 1-Gallon Solution Semi-Batch Reactor Propylene/EthylenePolymerization Procedure: Solution semi-batch reactor polymerization ofpropylene and ethylene are carried out in a 1 gallon metal autoclavereactor equipped with a mechanical stirrer, a jacket with circulatingheat transfer fluid, which can be heated or cooled in order to controlthe internal reactor temperature, an internal thermocouple, pressuretransducer, with a control computer and several inlet and output valves.Pressure and temperature are continuously monitored during thepolymerization reaction. Measured amounts of propylene are added to thereactor containing about 1000 g Isopar E as solvent. The reactor isheated up to the reaction temperature with stirring (typically about1,000 rpm or higher) and then the desired amount of ethylene is addedthrough a mass flow meter. The active catalyst is prepared in a dryboxby syringing together solutions of the appropriate catalyst, cocatalyst,and any scavenger (if desired) components with additional solvent togive a total volume which can be conveniently added to the reactor(typically 10–20 mL total). If desired, a portion of the scavenger(typically an aluminum alkyl, alumoxane, or other alkyl-aluminumcompound) may be added to the reactor separately prior to the additionon the active catalyst solution. The active catalyst solution is thentransferred by syringe to a catalyst addition loop and injected into thereactor over approximately 2.5 minutes using a flow of high pressuresolvent. Immediately following the desired polymerization time, stirringand heating are stopped. The polymer solution is then dumped from thereactor using a bottom-valve through a heated transfer line into anitrogen-purged glass kettle. An aliquot of the additive solutiondescribed above is added to this kettle and the solution stirredthoroughly (the amount of additive used is chosen based on the totalpolymer produced, and is typically targeted at a level of about1000–2000 ppm). The polymer solution is dumped into a tray, air driedovernight, then thoroughly dried in a vacuum oven for two days. Theweights of the polymers are recorded and the efficiency calculated asgrams of polymer per gram of transition metal.Homopolymerization of propylene using Catalyst H: Using the generalsolution semi-batch reactor polymerization procedure described above,507 g of propylene was added along with 1402 g of ISOPAR-E. This washeated to 110° C. A catalyst solution was prepared by combiningsolutions of Catalyst H, Armeenium borate, and PMAO-IP to give 3micromoles of Hf, 3 micromoles of Armeenium borate, and 600 micromolesof Al. The catalyst solution was added to the reactor as described inthe general procedure. After 10 minutes reaction time, the bottom valvewas opened and the reactor contents transferred to the glass kettle. Theadditive solution was added and the polymer solution was stirred to mixwell. The contents were poured into a glass pan, cooled and allowed tostand in a hood overnight, and dried in a vacuum oven for 2 days. Theisolated polymer yield was 50.1 grams. The Mw was 293,000 and the Mn was100,000. The polymer melting point was 144.4° C.

EXAMPLE 16

This example demonstrates the calculation of B values for certain of theExamples disclosed herein. The polymer from Comparative Example 1 isanalyzed as follows. The data was collected using a Varian UNITY Plus400 MHz NMR spectrometer, corresponding to a ¹³C resonance frequency of100.4 MHz. Acquisition parameters were selected to ensure quantitative¹³C data acquisition in the presence of the relaxation agent. The datawas acquired using gated ¹H decoupling, 4000 transients per data file, a7 sec pulse repetition delay, spectral width of 24,200 Hz and a filesize of 32K data points, with the probe head heated to 130° C. Thesample was prepared by adding approximately 3 mL of a 50/50 mixture oftetrachloroethane-d2/orthodichlorobenzene that is 0.025M in chromiumacetylacetonate (relaxation agent) to 0.4 g sample in a 10 mm NMR tube.The headspace of the tube was purged of oxygen by displacement with purenitrogen. The sample was dissolved and homogenized by heating the tubeand its contents to 150° C., with periodic refluxing initiated by heatgun.

Following data collection, the chemical shifts were internallyreferenced to the mmmm pentad at 21.90 ppm.

For propylene/ethylene copolymers, the following procedure is used tocalculate the percent ethylene in the polymer. Integral regions aredetermined as follows:

TABLE 16-1 Integral Regions for Calculating % Ethylene Regiondesignation Ppm Integral area A 44–49 259.7 B 36–39 73.8 C 32.8–34  7.72 P 31.0–30.8 64.78 Q Peak at 30.4 4.58 R Peak at 30 4.4 F 28.0–29.7233.1 G   26–28.3 15.25 H 24–26 27.99 I 19–23 303.1Region D is calculated as follows:D=P−(G−Q)/2.Region E is calculated as follows:E=R+Q+(G−Q)/2.The triads are calculated as follows:

TABLE 16-2 Traid Calculation PPP = (F + A − 0.5D)/2 PPE = D EPE = C EEE= (E − 0.5G)/2 PEE = G PEP = H Moles P = (B + 2A)/2 Moles E = (E + G +0.5B + H)/2

For this example, the mole % ethylene is calculated to be 13.6 mole %.

For this example, the triad mole fractions are calculated to be asfollows:

TABLE 16-3 Triad Mole Calculation PPP = 0.6706 PPE = 0.1722 EPE = 0.0224EEE = 0.0097 PEE = 0.0442 PEP = 0.0811

From this, the B value is calculated to be(0.172+0.022+0.044+0.081)/2(0.136×0.864)=1.36

In a similar manner, the B values for the following examples arecalculated to be:

TABLE 16-4 B-Value Calculation Example B Value Comparative 1 1.36 2 1.683 1.7 4 1.78 6 1.7

EXAMPLE 17

Table 17 is a summary showing the skewness index, S_(ix), for inventiveand prior art samples. All of the samples were prepared and measured asdescribed in Table C in the Description of the Preferred Embodiments andentitled Parameters Used for TREF. The copolymers of the invention havea skewness index greater than about (−1.2). The results from Table 17are represented graphically in FIG. 22.

The inventive examples show unusual and unexpected results when examinedby TREF. The distributions tend to cover a large elution temperaturerange while at the same time giving a prominent, narrow peak. Inaddition, over a wide range of ethylene incorporation, the peaktemperature, T_(Max), is near 60° C. to 65° C. In the prior art, forsimilar levels of ethylene incorporation, this peak moves to higherelution temperatures with lower ethylene incorporation.

For conventional metallocene catalysts the approximate relationship ofthe mole fraction of propylene, X_(p), to the TREF elution temperaturefor the peak maximum, T_(Max), is given by the following equation:Log_(e)(X _(p))=−289/(273+T _(max))+0.74

For the inventive copolymers, the natural log of the mole fraction ofpropylene, LnP, is greater than that of the conventional metallocenes,as shown in theis equation:LnP>−289/(273+T _(max))+0.75

TABLE 17 Summary of Skewness Index Results Elution Temperature Ethyleneof Peak Content maximum Inventive Catalyst Type (Mole %) (° C.)Inventive S_(ix) Sample 17-1 Catalyst H 8.2 61.4 0.935 Sample 17-2Catalyst J 8.9 60.8 −0.697 Sample 17-3 Catalyst J 8.5 61.4 −0.642 Sample17-4 Catalyst J 7.6 65.0 0.830 Sample 17-5 Catalyst J 7.6 65.0 0.972Sample 17-6 Catalyst J 8.6 61.4 0.804 Sample 17-7 Catalyst J 9.6 60.2−0.620 Sample 17-8 Catalyst J 12.4 60.2 0.921 Sample 17-9 Catalyst J 8.660.8 −0.434 Sample 17-10 Catalyst J 8.6 62.0 1.148 Sample 17-11 CatalystH 57.8 1.452 Sample 17-12 Catalyst J 78.2 1.006 Sample 17-13 Catalyst H4.4 80.0 −1.021 Sample 17-14 Catalyst E 7.6 80.6 −1.388 Sample 17-15Catalyst E 10.0 70.4 −1.278 Sample 17-16 Catalyst E 10.7 66.2 −1.318Sample 17-17 Catalyst F 11.1 69.2 −1.296 Sample 17-18 Catalyst E 10.665.6 −1.266

EXAMPLE 18

DSC analysis shows that propylene/ethylene copolymers produced by asolution polymerization process using a nonmetallocene, metal-centered,pyridal-amine ligand catalyst have melting behavior that differs insurprising ways from propylene/ethylene copolymers produced bymetallocene polymerization processes that are known in the art. Thedifferent melting behavior of these copolymers compared to that ofcopolymers that are known in the art not only demonstrates the noveltyof these materials, but also can be used to infer certain advantages ofthese materials for some applications. The novel aspects of the meltingbehavior of these copolymers and their associated utility are discussedbelow, after first describing the DSC analysis method.

Any volatile materials (e.g., solvent or monomer) are removed from thepolymer prior to DSC analysis. A small amount of polymer, typically fiveto fifteen milligrams, is accurately weighed into an aluminum DSC panwith lid. Either hermetic or standard type pans are suitable. The pancontaining the sample is then placed on one side of the DSC cell, withan empty pan with lid placed on the reference side of the DSC cell. TheDSC cell is then closed, with a slow purge of nitrogen gas through thecell during the test. Then the sample is subjected to a programmedtemperature sequence that typically has both isothermal segments andsegments where the temperature is programmed to increase or decrease ata constant rate. Results that are presented here were all obtained usingheat-flux type DSC instruments manufactured by TA Instruments (e.g.,Model 2910 DSC). The measurement principles underlying heat-flux DSC aredescribed on page 16 of Turi, ibid. The primary signals generated bysuch instruments are temperature (units: ° C.) and differential heatflow (units: watts) into or out of the sample (i.e., relative to thereference) as a function of elapsed time. Melting is endothermic andinvolves excess heat flow into the sample relative to the reference,whereas crystallization is exothermic and involves excess heat flow outof the sample. These instruments are calibrated using indium and othernarrow-melting standards. Calibration ensures that the temperature scaleis correct and for the proper correction of unavoidable heat losses.

Temperature programs for DSC analysis of semi-crystalline polymersinvolve several steps. Although the temperature programs used togenerate the data presented here differed in some details, the criticalsteps were maintained constant throughout. The first step is an initialheating to a temperature sufficient to completely melt the sample; forpolypropylene homopolymers and copolymers, this is 210° C. or higher.This first step also helps insure excellent thermal contact of thepolymer sample with the pan. Although details of this first stepdiffered for data presented here—for example, the rate of heating, theupper temperature, and the hold time at the upper temperature—in allcases the choices were sufficient to achieve the principal objectives ofthis step, of bringing all samples to a common completely meltedstarting point with good thermal contact. The second step involvescooling at a constant rate of 10° C./min from an upper temperature of atleast 210° C. to a lower temperature of 0° C. or less. The lowertemperature is chosen to be at or slightly below the glass transitiontemperature of the particular propylene polymer. The rate ofcrystallization becomes very slow at the glass transition temperature;hence, additional cooling will have little effect on the extent ofcrystallization. This second step serves to provide a standardcrystallization condition, prior to examining subsequent meltingbehavior. After a brief hold at this lower temperature limit, typicallyone to three minutes, the third step is commenced. The third stepinvolves heating the sample from a temperature of 0° C. or lower (i.e.,the final temperature of the previous step) to 210° C. or higher at aconstant rate of 10° C./min. This third step serves to provide astandard melting condition, as preceded by a standard crystallizationcondition. All the melting behavior results presented here were obtainedfrom this third step, that is, from the second melting of the sample.

The output data from DSC consists of time (sec), temperature (° C.), andheat flow (watts). Subsequent steps in the analysis of meltingendotherms are as follows. First, the heat flow is divided by the samplemass to give specific heat flow (units: W/g). Second, a baseline isconstructed and subtracted from the specific heat flow to givebaseline-subtracted heat flow. For the analyses presented here, astraight-line baseline is used. The lower temperature limit for thebaseline is chosen as a point on the high temperature side of the glasstransition. The upper temperature limit for the baseline is chosen as atemperature about 5–10° C. above the completion of the meltingendotherm. Although a straight-line baseline is theoretically not exact,it offers greater ease and consistency of analysis, and the errorintroduced is relatively minor for samples with specific heats ofmelting of about 15–20 Joules per gram or higher. Employing astraight-line baseline in lieu of a more theoretically correct baselinedoes not substantively affect any of the results or conclusionspresented below, although the fine details of the results would beexpected to change with a different prescription of the instrumentalbaseline.

There are a number of quantities that can be extracted from DSC meltingdata. Quantities that are particularly useful in demonstratingdifferences or similarities among different polymers are: (1) the peakmelting temperature, T_(max) (° C.), which is the temperature at whichthe baseline-subtracted heat flow is a maximum (here the convention isthat heat flow into the sample is positive); (2) the specific heat ofmelting, Δh_(m) (J/g), which is the area under the melting endothermobtained by integrating the baseline-subtracted heat flow (dq/dt) (W/g)versus time between the baseline limits; (3) the specific heat flow(dq/dt)_(max) (W/g) at the peak melting temperature; (4) the peakspecific heat flow normalized by the specific heat of melting,{(dq/dt)_(max)/Δh_(m}(sec) ⁻¹); (5) the first moment T¹ of the meltingendotherm, defined and calculated as described below; (6) the varianceV₁ (° C²) of the melting endotherm relative to the first moment T₁,defined and calculated as described below; and (7) the square root ofthe variance, V₁ ^(1/2) (° C.), which is one measure of the breadth ofthe melting endotherm.

Treatment of the melting endotherm as a distribution is a useful way toquantify its breadth. The quantity that is distributed as a function oftemperature is the baseline-subtracted heat flow (dq/dt). That this isalso a distribution of temperature is made explicit using the calculuschain rule, (dq/dt)=(dq/Dt)(Dt/dt) where (Dt/dt) is the heating rate.The standard definition of the first moment T₁ of this distribution isgiven by the following equation, where the integrations are carried outbetween the baseline limits. All integrations are most reliablyperformed as (dq/dt) versus time, as opposed to the alternative (dq/Dt)versus temperature. In the following equation, (dq/dt) and T are thespecific heat flow and temperature at time t.

$T_{1} = \frac{{\int T}{{\cdot ( {{\mathbb{d}q}/{\mathbb{d}t}} )}{\mathbb{d}t}}}{\int{( {{\mathbb{d}q}/{\mathbb{d}t}} ){\mathbb{d}t}}}$

The variance V₁ relative to the first moment is then standardly definedas:

$V_{1} = \frac{\int{{( {T - T_{1}} )^{2} \cdot ( {{\mathbb{d}q}/{\mathbb{d}t}} )}{\mathbb{d}t}}}{\int{( {{\mathbb{d}q}/{\mathbb{d}t}} ){\mathbb{d}t}}}$

Both V₁ and V₁ ^(1/2) are measures of the breadth of the meltingendotherm.

Results of DSC analyses of both inventive and comparative polymers areshown in Table 18-1. All the samples are propylene/ethylene copolymers,with the exception of Samples 1–4 and 17 which are homopolymers.Polymers 1–16 were made using Catalyst H in a solution process. Polymers17–27 were made with Catalyst E in a solution process. An idea of theprecision of the experimental method plus the data analysis procedure isprovided by replicates (polymers 17, 20, and 22) and by the consistencyof results for sets of polymers that were synthesized under nearlyidentical conditions (polymers 1–4,7–9, 10–12, and 13–16).

Differences in melting behavior are most easily seen with the aid offigures. FIG. 24 compares the melting endotherms of Samples 8 and 22a.These two propylene/ethylene copolymers have nearly equivalent heats ofmelting and mole percent ethylene contents, about 71 J/g and 8 mole %.However, despite these similarities, the melting behavior of theinventive copolymer (Sample 8) is surprisingly different than that ofthe comparative copolymer (Sample 22a). The melting endotherm of Sample8 is shifted towards lower temperatures and significantly broadened,when comparing at equivalent heat of melting. These changes in meltingbehavior are unique to and characteristic of the copolymers of thisinvention.

Comparison at equivalent heats of melting is particularly meaningful andrelevant. This is because equivalent heats of melting impliesapproximately equal levels of crystallinity, which in turn implies thatthe room temperature moduli should be similar. Therefore, at a givenmodulus or stiffness, the copolymers of this invention possess usefullybroadened melting ranges compared to typical non-inventive copolymers.

FIGS. 25–29, which are derived from the results in Table 18-1, furtherhighlight the differences in melting behavior for the copolymers of thisinvention compared to typical copolymers. For all five of these figures,quantities are plotted as functions of the heat of melting, which asdescribed above is an especially meaningful and relevant basis formaking intercomparisons and inferring utility. For these plots, datahave broken into two series based on the catalyst type used to make thepolymer, either metallocene or nonmetallocene type.

FIG. 25 demonstrates how the peak melting temperature is shifted towardslower temperature for the copolymers of this invention. All the changesin melting behavior, of which this shift in peak melting temperature isbut one example, imply that there are differences in the crystallinestructure at the level of crystal lamellae or other type of primarycrystalline elements. In turn, such differences in crystalline structurecan most reasonably be attributed to differences in microstructure, forexample, the different type of mis-insertion errors or the higher Bvalues that characterize the polymers of this invention. Regardless ofthe exact nature of the microstructural features that give rise to thechanges in melting behavior, the changes are in and of themselvesevidence that the copolymers of this invention are novel compositions.

FIG. 26 which shows a plot of the temperature T_(1% c) at which there isapproximately 1% residual crystallinity, demonstrates another surprisingaspect of the melting behavior of the copolymers of this invention. Thefactor that is used to convert specific heat of melting into nominalweight % crystallinity is 165 J/g=100 weight % crystallinity. (Use of adifferent conversion factor could change details of the results but notsubstantive conclusions.) With this conversion factor, the totalcrystallinity of a sample (units: weight % crystallinity) is calculatedas 100% times Δh_(m) divided by 165 J/g. And, with this conversionfactor, 1% residual crystallinity corresponds to 1.65 J/g. Therefore,T_(1% c) is defined as the upper limit for partial integration of themelting endotherm such that Δh_(m) minus the partial integral equals1.65 J/g, where the same lower limit and baseline are used for thispartial integration as for the complete integration. Surprisingly, fornonmetallocene-catalyzed copolymers as compared to metallocene-catalyzedcopolymers, this 1% residual crystallinity temperature shifts downwardless rapidly with increase in ethylene level (i.e., with decrease in theheat of melting). This behavior of T_(1% c) is similar to that of thefinal temperature of melting T_(me).

FIG. 27, which shows the variance relative to the first moment of themelting endotherm as a function of the heat of melting, demonstratesdirectly the greater breadth of the melting endotherm for the copolymersof this invention.

FIG. 28, which shows the maximum heat flow normalized by the heat ofmelting as a function of the heat of melting, further demonstrates thebroadening of the melting endotherm. This is because, at equivalent heatof melting, a lower peak value implies that the distribution must bebroadened to give the same area. Roughly approximating the shape ofthese melting curves as a triangle, for which the area is given by theformula one-half times the base times the height, then b1/b2=h2/h1. Theinventive copolymers show as much as a four-fold decrease in height,implying a significant increase in breadth.

FIG. 29 illustrates a useful aspect of the broader melting range of theinventive polymers, namely that the rate at which the last portion ofcrystallinity disappears (units: weight % crystallinity per ° C.) issignificantly lower than for metallocene polymers.

The data in Table 18-2 demonstrate in practical terms the utility ofthis broadening of the melting endotherm. Entries in Table 18-2illustrate: (1) the extent to which a greater fraction of melting occursat lower temperatures, which is important for heat seal and bondingapplications, and which is greater for the inventive copolymers; and (2)the extent to which crystallinity remains at higher temperatures and therate at which the final portion of crystallinity disappears, which canbe important for fabrication operations such as thermoforming, foaming,blow molding, and the like, both of which are greater for the inventivecopolymers.

TABLE 18-1 Melting Results from DSC ethylene Δh_(m) T_(max) T₁(dq/dt)_(max)/Δh_(m) V₁ T_(1% c) Sample* (mole %) (J/g) (° C.) (° C.)(sec⁻¹) (° C.²) (° C.) R_(f) (**) 18-1-1 0.0 90.4 139.0 123.5 0.0109 416143.0 1.60 18-1-2 0.0 94.3 138.8 122.2 0.0105 505 143.1 1.54 18-1-3 0.094.0 139.4 122.4 0.0105 505 143.3 1.60 18-1-4 0.0 95.9 139.5 121.40.0102 576 143.4 1.60 18-1-5 1.5 92.4 138.2 118.4 0.0105 630 142.0 1.4818-1-6 4.3 85.0 120.7 99.2 0.0045 716 135.0 0.40 18-1-7 8.2 67.5 85.983.8 0.0023 909 139.7 0.19 18-1-8 8.2 71.2 93.0 84.4 0.0025 835 137.50.19 18-1-9 8.2 74.6 108.2 87.0 0.0029 790 134.6 0.23 18-1-10 11.8 51.671.7 69.3 0.0024 790 124.4 0.14 18-1-11 11.8 52.5 74.8 69.4 0.0025 781123.7 0.14 18-1-12 11.8 51.9 73.9 69.4 0.0025 802 124.3 0.14 18-1-1315.8 24.0 55.2 66.7 0.0031 667 112.0 0.10 18-1-14 15.8 28.7 55.2 66.30.0026 795 118.0 0.10 18-1-15 15.8 27.6 55.6 66.0 0.0026 783 116.4 0.1018-1-16 15.8 26.9 55.2 66.4 0.0026 769 115.7 0.10 18-1-17a 0.0 120.7160.3 145.3 0.0104 457 165.9 1.43 18-1-17b 0.0 123.9 159.8 144.5 0.0105486 165.2 1.54 18-1-18 . . . 90.3 140.6 125.0 0.0076 419 146.1 1.2118-1-19 . . . 91.3 139.0 123.9 0.0068 374 145.5 1.05 18-1-20a 4.2 110.2137.7 121.8 0.0094 337 144.3 0.95 18-1-20b 4.2 96.5 137.9 121.1 0.0100451 142.7 1.38 18-1-21 . . . 94.6 136.7 120.3 0.0086 385 140.5 1.4318-1-22a 8.0 71.4 117.5 105.8 0.0081 197 124.8 0.74 18-1-22b 8.0 69.7117.0 103.4 0.0080 271 122.8 1.00 18-1-23 . . . 70.1 110.3 91.0 0.0062512 115.9 0.95 18-1-24 . . . 55.9 97.0 78.7 0.0052 436 103.9 0.6718-1-25 . . . 19.8 63.0 61.1 0.0044 188 80.1 0.25 18-1-26 . . . 18.256.6 58.8 0.0049 158 75.3 0.27 *Samples 18-1-1 to −4 made with catalystG, samples −5 to −16 with catalyst H, and −17 to −24 with catalyst E.**Units for R_(f): weight % crystallinity per °C.

TABLE 18-2 Broadening of the Melting Endotherm starting Fractionfraction Fraction fraction crystallinity Melted Melted Remainingremaining Sample (weight %) at T₁ − 30° C. at T₁ − 20° C. at T₁ + 20° C.at T₁ + 30° C. 18-2-8 (inventive) 43.2 0.153 0.229 0.249 0.134 18-2-22a(comparative) 43.3 0.040 0.112 0.019 0.004 18-2-11 (inventive) 31.80.143 0.235 0.221 0.131 18-2-25 (comparative) 33.9 0.103 0.170 0.1270.009

EXAMPLE 19

The data of Table 19-1 shows that at the same level of haze (about 11%),the inventive P/E* polymer (19-1-1) has an equivalent modulus to acomparable metallocene catalyzed propylene/octene/ethylene terpolymer(P/O/E) polymer, with somewhat better toughness.

The data of Table 19-1 also shows that at the same level of haze (about11%), the inventive P/E* polymer is about nine times more flexible andis much tougher (about 40 C higher ductile brittle transitiontemperature (DBTT)) than a Ziegler-Natta catalyzed P/E.

The data of Table 19-2 shows that the inventive P/E* polymers exhibit awide TMA range of 147–55 C, with an expected lowering of the TMA inresponse to an increasing ethylene content, and a similar TMA toethylene-octene polymer (AFFINITY EG8100 shown in Table 19-3) atequivalent crystallinity. In this table, “crystallinity from density”was determined as follows:

${{Crystallinity}\mspace{14mu}{fromdensity}} = {( \frac{0.936}{sampledensity} ) \times ( \frac{{sampledensity} - 0.853}{0.083} ) \times 100}$

The data of Table 19-2 also shows not only that the inventive P/E*polymers exhibit a wide flexural modulus range, i.e., 1.6 to 195 kpsi,based on their respective ethylene contents, but also a higher modulusthan ethylene-octene polymer (AFFINITY EG8100 shown in Table 19-3) atequivalent crystallinity.

TABLE 19-1 Comparative Injection Molded Properties of Various P/EPolymers Flex. Mod. Ethylene MFR Haze (1% sec., DBTT Tm NumberDescription (mol %) (g/10 min) (%) kpsi) (° C., Dyn.) (° C.) 19-1-1 P/E*via Catalyst H 11.8 2.2 11.6 19.5 −20 121 19-1-2 P/O/E via Catalyst E7.8 O + 1.3 E 1.1 10.8 20 −13 80 19-1-3 Basell Profax  4.4 2.0 11.3 16920 150 SR256M19-1-2 is a Propylene-Octene-Ethylene copolymer prepared in solution viaCatalyst H, containing 7.8 mol % octene and 1.3 mol % ethylene, with anMFR of 1.1 g/10 min.

TABLE 19-2 Comparative Injection Molding Properties of Various P/E andE/O Polymers Flex. Cryst. (%) Mod. Ethylene From (1% sec., TMA NumberDescription (mol %) density kpsi) (° C., 1 mm) 19-2-1 HPP via 0.0 61.4195 147 Catalyst H 19-2-2 P/E* via 8.2 40.8 48 106 Catalyst H 19-2-3P/E* via 11.8 27.2 19.5 87 Catalyst H 19-2-4 P/E* via 15.8 15.4 5.6 70Catalyst H 19-2-5 P/E* via 18.6 6.7 1.6 55 Catalyst H

TMA, “thermal mechanical analysis”, is the upper service temperaturedetermined from a thermal mechanical analyzer (Perkin-Elmer TMA 7series) scanned at 5 C/min and a load of 1 Newton, and defined as thetemperature at which the probe penetrates 1 mm into the sample.

TABLE 19-3 Comparative Injection Molding TMA Properties of Certain P/Eand E/O Polymers Flex. Cryst. (%) Mod. Ethylene from (1% sec., TMANumber Description (mol %) density kpsi) (° C., 1 mm) 19-3-1 P/E* via15.8 15.4 5.6 70 Catalyst H 19-3-2 AFFINITY 82.9 11.9 2.4 68 EG8100

EXAMPLE 20

The inventive polypropylenes reported in Table 20-1 were made accordingto the teachings of the present invention in a continuous solutionprocess. These polymers were fed into a Killion blown film lineavailable from Killion Extruders INC. under model designation KN-125.During the film blowing, the Killion line was equipped with a 1.5 inch(3.81 cm) diameter screw, 3 inch (7.62 cm) die diameter, and a 70 mil(1778 micron) die gap. The extruder is 50 inch (125 cm) long with alength to diameter ratio (L/D) of 30. The melt temperature was about 425F (218.2 C) with a blow-up ratio (BUR) of 2.0 and an output rate of 10lb/h.

The resulting films were 2.0 mil (50 micron) in thickness and filmproperties were measured according to the standard ASTM methods reportedin Table 20-2.

For comparison, various commercially or experimentally availableZiegler-Natta catalyzed polypropylene resins, also reported in Table20-1, were also fabricated with the Killion line under operatingparameters similar to those used for the inventive polymers. Filmproperties were also measured according to the standard ASTM methodsreportred in Table 20-2.

Film properties for all above films are shown in Table 20-3 and thehaze, CD and MD-tear (cross and machine direction, respectively), gloss45 and dart data are plotted in FIGS. 16–18 and 30–31. These Figuresclearly demonstrate that films made by the polypropylene of thisinvention have better haze, CD and MD-tear, gloss-45 and dart propertiesthan existing Ziegler-Natta polypropylene with similar comonomercontent. Moreover, the hot tack and heat sealing properties of the filmswere measured, and the results are reported in FIGS. 19 and 20,respectively. Here too, the polymers of this invention exhibitedsuperior properties to those of a Z-N catalyzed propylene/ethylenecopolymer (even though the Z-N copolymer contained a larger amount ofethylene).

In an alternative embodiment of this invention, a commercially availableZiegler-Natta polypropylene, namely H308-02Z produced by the DowChemical Company, was used as based resin for a blending study. Variousinventive polypropylenes and commercially/experimentally availablepolypropylene resins were dry blended with the Z-N catalyzedpolypropylene with a weight ratio of 70/30 for Z-N polypropylenes. Theabove dry blended materials were fed into the Killion line, as describedabove, to produce blown films and the film properties were measured asdescribed above.

Film properties for these blended films are reported in Table 20-4 andFIGS. 32–36. As can be seen from this data, the films made by blending30% of inventive polypropylene with 70% of the commercial Z-Npolypropylene have much better properties than similar films made byblending other Z-N polypropylenes with the H308-02Z.

TABLE 20-1 Resins co-monomer Co- Resins MFR type monomer % 20-1-1 2 020-1-2 2 Ethylene 3 Inventive copolymer 20-1-3 2 Ethylene 5 Inventivecopolymer 20-1-4 2 Ethylene 8 Inventive copolymer 20-1-5 2 Ethylene 11Inventive copolymer Manufacture/Trade name 20-1-6 2 Ethylene 0.5 Dow,PP, H308-02Z 20-1-7 2 Ethylene 3 Basell, PP, SR256M 20-1-8 7 Ethylene5.5 Dow, PP, DS6082, propylene-butene copolymer 20-1-9 2 Ethylene 3 Dow,PP, 6D69 20-1-10 5 1-Butene 12 Dow, PP*

TABLE 20-2 Test Test Methods Dart-A ASTM D-1709 Elmendorf Tear-B ASTMD1922 Haze ASTM D1003 Tensile, ASTM D822 Gloss-45 degree ASTM D2457 MFRASTM 1238 Heat Seal DOW* Hot tack DOW** *The term “Heat seal” is used asan expression for the strength of the heat seal after they have beenallowed to cool. It should be pointed out that heat seal samples areconditioned in the laboratory for twenty four hours before they aretested on the Instron. Film samples size is 1 inchwide by 12.5 inch longfor testing. The sealing time is 0.5 seconds, sealing pressure is 0.275N/mm², the delay time is 0.1 second, the peel speed is 200 mm/second andthe seal bars are 5 mm wide. The seal temperature varies based uponpolymer properties. Usually, 5 samples are tested. **The term “Hot Tack”is used as an expression for the strength of the heat seals immediatelyafter the sealing operating and before the seal has had a chance tocool. All testing procedures for hot tack is similar to that of heatseal except it is tested right after films have been sealed.

TABLE 20-3 File Property Comparison of Neat PP Resins Wt %Resin/properties comonomer MD-tear, g CD-tear, g Dart, g Haze, %Gloss-45 20-1-1 0 13 25 60 28 30 20-1-2 3 16 52 60 5.5 75 20-1-3 5 2901063 640 5 74 20-1-4 8 740 1327 756 2 88 20-1-6 0.5 14 46 60 34 2320-1-7 3 19 56 60 20-1-8 3.2 20-1-9 5.5 23 43 68 10 68 20-1-10 12 23 4368 10 68

TABLE 20-4 Comparison of Film Properties of Blended PP Resins CD- CD-Resin/properties MD-tear, g CD-tear, g Dart, g elongation, % Ultimate,psi (70/30) Sample 20- 36 75 89 843 6212 1-6/Sample 20-1-4 (70/30)Sample 20- 50 243 117 805 6015 1-6/Sample 20-1-5 (70/30) Sample 20-1- 1656 60 10 4672 6/Dow PP SRD4190 (70/30) Sample 20-1- 17 47 60 10 45806/Sample 20-1-8

EXAMPLE 21

Table 21 reports the details behind FIGS. 13–16. All these samples weremade by a solution polymerization process. Homopolymer samples 21-1 and21-12 were made with catalysts E and G, respectively. Comparativemetallocene propylene/ethylene copolymer samples 21-2 through 21-11 weremade with catalyst E. Non-metallocene propylene/ethylene copolymersamples 21-13 through 21-16 were made with catalyst H. Mole % ethylenewas determined by ¹³C-NMR. T_(max) was determined by DSC, second heatingscan at 10° C./min. Flexural modulus values in Table 21 are either from:(a) direct measurement on injection molded specimens by ASTM D790(samples marked by asterisks); or (b) measurement of tensile modulus oncompression molded microtensile specimens by ASTM D638 then use ofestablished correlations between tensile and flexural moduli to estimatethe flexural modulus; or (c) estimation of flexural modulus fromcorrelations of flexural modulus to heat of fusion by DSC. Haze wasmeasured on 10 mil thick compression molded films by ASTM D1003 usingModel XC211 Haze-Gard System manufactured by Pacific Scientific,Gardner/Neotec Instrument Division. Films for haze measurements werecompression molded at 200° C. with six minute preheat at low pressureplus four minute molding at about 200 psi pressure, followed by tenminute cooling to 30° C. at 200 psi pressure. Mylar film was used asbacking in contact with the polymer in order to obtain films withminimal surface haze. After molding, films or other specimens were agedtwo weeks or longer at room temperature prior to mechanical testing orhaze testing.

TABLE 21 Data for FIGS. 13–16 Sample Mole % E T_(max) (° C.) E_(flex)(ksi) % Haze 21-1* 0 154 216 49.5 21-2 2.6 147 183 31.2 21-3 3.4 142 16329.1 21-4 5.1 132 122 30.0 21-5 5.5 131 118 30.4 21-6* 6.5 120 91 30.821-7* 7.2 120 83 34.2 21-8 9.8 113 63 30.6 21-9 12.3 94 26 24.4 21-1014.6 81 14 20.6 21-11 17.4 66 12 21.3 21-12* 0 144 195 33.3 21-13 8.2104 57 27.0 21-14* 11.8 68 20 22.3 21-15* 15.8 54 5.6 14.0 21-16* 18.639 1.6 13.2

EXAMPLE 22

FIGS. 14 and 15 report certain elasticity data for the polymers of thisinvention and certain comparative polymers. Table 22-1 describes theelastomers.

The test samples were compression molded specimens. Polymer in pelletform was compression molded at 190 C into 1.5 mm thick sheets. Thesheets were cooled by placing each between two platens at 25 C underlight pressure. The specimens were allowed to age for at least sevendays at ambient conditions before testing.

Tensile “dog bones” were punched out of the sheets using a knife shapedaccording to ASTM D-1708. The first melting behavior was measured bycutting out a 5 to 10 mg piece of the aged specimen. The specimen wasloaded into an aluminum pan and analyzed in a differential scanningcalorimeter manufactured by TA Instruments Incorporated. Heating spanned−50 to 230 C at 10° C./min.

The specimens were tested in uniaxial tension with a mechanical testdevice (Instron Corp.) fitted with pneumatic grips. The engineeringstrain rate was 400% per minute. Both strain to break and multicycleloading strain histories were used. In the case of multicycle loading,specimens were loaded and unloaded to various strains (100 to 900%) forup to 10 cycles. No pause was used between successive cycles.

Table 22-2 reports the data in FIGS. 14 and 15. The data in Table 22-2reports elasticity versus crystallinity for the same group ofelastomers. Crystallinity is an important property in elastomericapplications because it controls to a large extent the stiffness (i.e.,modulus) of a material. The virgin or unstretched metallocenepolypropylenes exhibit elasticity versus crystallinity similar to thehomogeneous polyethylene and ethylene-stryene elastomers, while theelastomeric polymers of this invention exhibit higher elasticity at thesame crystallinity. Even after pre-stretching, the elastomeric polymersof this invention continue to exhibit superior elasticity at the samecrystallinity as compared to both the metallocene propylenes and thehomogeneous polyethylene and ethylene-stryene elastomers. The polymersof this invention demonstrate similar elasticity after stretching as docommercial grade SEBS polymers, e.g., Krayton G-1657.

TABLE 22-1 Elastomers DSC Polymer Copolymer Crystallinity samplesDescription (wt. %) (mol %) (wt. %) 1 inventive polymer 11 16 18 2inventive polymer 13 19 10 A metallocene propylene- — — 21 ethylenecopolymer B metallocene propylene- — — 4 ethylene copolymer Cdevelopmental ethylene- 41 15 14 octene copolymer5 D Affinity EG8100 3512 6 E developmental ethylene- 41 16 5 styrene copolymer F Kraton G-1657(SEBS) — — —

TABLE 22-2 Elasticity Values of the Data in FIGS. 14 and 15 virginpre-stretched average Polymer 1st cycle 10th cycle (>1 cycle) 1 0.570.88 0.88 2 0.75 0.97 0.97 A 0.49 0.85 0.83 B 0.71 0.99 0.99 C 0.52 0.780.76 D 0.64 0.92 0.89 E 0.71 0.92 0.90 F 0.90 0.98 0.99

EXAMPLE 23

This example demonstrates the use of a continuous 2-reactor solutionprocess in series wherein a higher modulus polypropylene is produced inthe first reactor, a lower modulus propylene/ethylene copolymer isprepared in series in a second reactor, and the solvent and unreactedmonomers are recycled to the reactors. The catalyst for this example isCatalyst J. Catalyst J can be made in an analogous manner to Catalyst H,excepting that 2-methyl-bromobenzene is used instead of9-bromophenanthrene.

Purified ISOPAR-E solvent, ethylene, hydrogen, and 1-octene are suppliedto a 1 gallon jacketed reactor equipped with a jacket for temperaturecontrol and an internal thermocouple. The solvent feed to the reactor ismeasured by a mass-flow controller. A variable speed diaphragm pumpcontrols the solvent flow rate and increases the solvent pressure to thereactor. The compressed, liquified propylene feed is measured by a massflow meter and the flow is controlled by a variable speed diaphragmpump. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst injection line and the reactor agitator.The remaining solvent is combined with ethylene and hydrogen anddelivered to the reactor. The ethylene stream is measured with a massflow meter and controlled with a Research Control valve. A mass flowcontroller is used to deliver hydrogen into the ethylene stream at theoutlet of the ethylene control valve. The temperature of thesolvent/monomer is controlled by use of a heat exchanger before enteringthe reactor. This stream enters the bottom of the reactor. The catalystcomponent solutions are metered using pumps and mass flow meters, andare combined with the catalyst flush solvent. This stream enters thebottom of the reactor, but in a different port than the monomer stream.The reactor is run liquid-full at 500 psig with vigorous stirring. Theprocess flow is in from the bottom and out of the top. All exit linesfrom the reactor are steam traced and insulated. The exit of the firstreactor is connected by insulated piping to a second 6 gallon reactorsimilarly equipped to the first, with a provision for independentcatalyst and cocatalyst addition, and additional monomer, hydrogen,solvent addition and jacket temperature control. After the polymersolution stream exits the second reactor, polymerization is stopped withthe addition of a small amount of water, and other additives andstabilizers can be added at this point. The stream flows through astatic mixer and a heat exchanger in order to heat the solvent/polymermixture. The solvent and unreacted monomers are removed at reducedpressure, and the product is recovered by extrusion using adevolatilizing extruder. The solvent and unreacted monomers arecondensed and recovered into a storage tank, from which they can bepumped (optionally with the addition of fresh solvent, propylene, and/orother monomers) back to the first and/or the second reactor. Theextruded strand is cooled under water and chopped into pellets. Theoperation of the dual-reactor system is controlled with a processcontrol computer.

A 4 L catalyst tank is filled with an ISOPAR E solution of Catalyst J ata concentration of 50 ppm Hf. Additional tanks are provided with asolution of N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)boratein ISOPAR E at a concentration of 100 ppm B, and MMAO-3A in ISOPAR E ata concentration of 100 ppm Al. ISOPAR E is continuously fed into thefirst reactor, along with propylene. The Catalyst J solution, along withenough N,N-dioctadecylanilinium tetrakis(pentafluorophenyl)borate inISOPAR E and MMAO-3A in ISOPAR E to maintain a Hf:B:Al molar ratio of1:1.2:5 is added to the first reactor. The solvent and propylene feedrate, as well as the jacket temperature and catalyst feed rate areadjusted to produce 1.5 pounds per hour of a propylene polymer having amelting point >140 degrees C. The flow rate of Catalyst J is adjusted tomaintain a first-reactor product melt flow rate (MFR) of 2.0, whilemaintaining 50% propylene conversion at 16 weight % polymer in solutionand a reactor temperature of 100 degrees C. by adjusting the temperatureof the reactor jacket, the feed temperature and through the addition ofhydrogen as a molecular weight control agent. The molar ratio ofaluminum can be adjusted in order to optimize the overall catalystefficiency. The contents of the first reactor flow into the secondreactor, where additional solvent and a mixture of propylene andethylene is added at a feed temperature of 5 degrees C. The Catalyst Jsolution, along with enough N,N-dioctadecylaniliniumtetrakis(pentafluorophenyl)borate in ISOPAR E and MMAO-3A in ISOPAR E tomaintain a Hf:B:Al molar ratio of 1:1.2:5 is added to the second reactorat a rate sufficient to maintain a 65% propylene conversion and areaction temperature of 110° C., with an overall production rate (thecombination of the product of reactor 1 and reactor 2) of 5 pounds perhour. The ethylene feed rate is adjusted to produce a second reactorproduct that is 8 weight % ethylene. This corresponds to a reactor splitof 30% (1.5 pounds/hr from the first reactor out of 5 pounds/hroverall). The flow rate of Catalyst J is adjusted to maintain an overallproduct melt flow rate (MFR) of 2.0 by adjusting the temperature of thereactor jacket and through the addition of hydrogen as a molecularweight control agent. The ethylene conversion into polymer is >96%. Themolar ratio of aluminum can be adjusted in order to optimize the overallcatalyst efficiency. After the post-reactor deactivation of thecatalyst, antioxidant is added, and the product is devolatilized andextruded to recover the solid product. The solvent and unreactedmonomers, which contain very low levels of unreacted ethylene, arecondensed, recovered, and can be pumped back into reactor 1 and reactor2 in a continuous process. Because most of the ethylene is consumed inthe second reactor, very little is recycled to the first reactor and themelting point and modulus of the polymer produced there is relativelyhigh. The product, which is a solution blend of 30 weight % high meltingpolypropylene (containing trace amounts of ethylene) having a 2 MFR and70 weight % of a 9 weight % ethylene/propylene copolymer, with theoverall product having a 2 MFR. This product is useful in a variety ofapplications, including BOPP (biaxially-oriented polypropylene) sealantsand films.

EXAMPLE 24

The procedure of Example 23 is followed, except that the first reactoris used to produce a copolymer of ethylene and propylene, and the secondreactor is used to produce a lower melting copolymer of propylene andethylene. For this example, the general procedure of Example A isfollowed except that the feeds are adjusted so that the first reactorproduces 1.5 pounds/hr of a copolymer of propylene with 2 weight %ethylene, having an MFR of 2. The first reactor temperature is 90degrees C. and the first reactor propylene conversion is 65%. At thispropylene conversion, the ethylene conversion can be >98%. The contentsof the first reactor, along with fresh catalyst and fresh propylene inadditional solvent at 5° C. passes into the second reactor. Additionalethylene is added to the second reactor in order to produce a 8 weight %ethylene copolymer in the second reactor at a reactor temperature of110° C., with a 30% reactor split and an overall isolated product of 2MFR. This product is particularly useful for BOPP.

EXAMPLE 25

The procedure of Example 23 is followed, except that the first reactoris used to produce a high molecular weight copolymer of ethylene andpropylene, and the second reactor is used to produce a high meltingpolymer of propylene of lower molecular weight. For this example, thegeneral procedure of Example 23 is followed except that the feeds areadjusted so that the first reactor produces 1.5 pounds per hour of acopolymer of propylene with 8 weight % ethylene, having an MFR of 0.1.The first reactor temperature is 90° C. and the first reactor propyleneconversion is 65%. At this propylene conversion, the ethylene conversioncan be >98%. The contents of the first reactor, along with freshcatalyst and fresh propylene in additional solvent at 5° C. passes intothe second reactor. The feeds to the second reactor are adjusted inorder to produce a high melting propylene polymer in the second reactorat a reactor temperature of 110° C., with a 30% reactor split and anoverall isolated product of 2 MFR. This product is particularly usefulfor thermoforming and extrusion blowmolding.

EXAMPLE 26

For this example, the general procedure of Example 25 is followed exceptthat the feeds are adjusted so that the first reactor produces 1.5pounds/hr of a copolymer of propylene with 13 weight % ethylene, havingan MFR of 0.1. The first reactor temperature is 90° C. and the firstreactor propylene conversion is 65%. At this propylene conversion, theethylene conversion can be >98%. The contents of the first reactor,along with fresh catalyst and fresh propylene in additional solvent at5° C. passes into the second reactor. The feeds to the second reactorare adjusted in order to produce a high melting propylene polymer in thesecond reactor at a reactor temperature of 110° C., with a 30% reactorsplit and an overall isolated product of 2 MFR. This product isparticularly useful for thermoforming and extrusion blowmolding.

EXAMPLE 27

For this example, the general procedure of Example 25 is followed exceptthat the feeds are adjusted so that the first reactor produces acopolymer of propylene with 13 weight % ethylene, having an MFR of 25.The first reactor temperature is 90° C. and the first reactor propyleneconversion is 65%. At this propylene conversion, the ethylene conversioncan be >98%. The contents of the first reactor, along with freshcatalyst and fresh propylene in additional solvent at 5° C. passes intothe second reactor. The feeds to the second reactor are adjusted inorder to produce a high melting propylene polymer in the second reactorat a reactor temperature of 110 degrees C., with a 30% reactor split andan overall isolated product of 25 MFR. This product is particularlyuseful for producing fibers.

EXAMPLE 28

The general procedure of Example 23 is followed except that the feedsare adjusted so that the first reactor produces a high melting propylenepolymer having an MFR of 25. The first reactor temperature is 90° C. andthe first reactor propylene conversion is 55%. The contents of the firstreactor, along with fresh catalyst and fresh propylene and ethylene inadditional solvent at 5° C. passes into the second reactor. The feeds tothe second reactor are adjusted in order to produce a propylene/ethylenecopolymer polymer in the second reactor at a reactor temperature of 110°C., with a 30% reactor split and an overall isolated product of 25 MFR.This product is particularly useful for producing fibers.

Although the invention has been described in considerable detail, thisdetail is for the purpose of illustration. Many variations andmodifications can be made on the invention as described above withoutdeparting from the spirit and scope of the invention as described in theappended claims. All publications identified above, specificallyincluding all U.S. patents and allowed U.S. patent applications, areincorporated in their entirety herein by reference.

1. A copolyrner of propylene and an unsaturated monomer other thanethylene, the copolymer comprising at least about 60 weight percent ofunits derived from propylene and at least about 0.1 weight percent ofunits derived from the unsaturated monomer, the copolymer characterizedas having ¹³C NMR peaks corresponding to a regio-error at about 14.6 andabout 15.7 ppm, the peaks of about equal intensity.
 2. The copolynier ofclaim 1 further characterized as having a skewness index, S_(ix),greater than about −1.20.
 3. The copolymer of claim 1 furthercharacterized as having a DSC curve with a T_(me) that remainsessentially the same and a T_(max) that decreases as the amount ofcomonomer other than ethylene in the copolymer is increased.
 4. Thecopolymer of claim 2 further characterized as having a DSC curve with aT_(me) that remains essentially the same and a T_(max) that decreases asthe amount of comonomer other than ethylene in The copolyri-ier isincreased.
 5. A fabricated article made from the copolymer of claim 1.6. The fabricated article of claim 5 in the form of a film.
 7. Thefabricated article of claim 5 in the form of a film.
 8. The fabricatedarticle of claim 5 in the form of a molded article.
 9. The fabricatedarticle of claim 5 in the form of a foam.
 10. The fabricated article ofclaim 5 in the form of a sheet.
 11. A blend of at least two polymers inwhich at least one polymer (a) comprises at least about 60 weightpercent of units derived from propylene and at least about 0.1 weightpercent of units derived from an unsaturated monomer other thanethylene, and (b) is characterized as having ¹³C NMR peaks correspondingto a regio-error at about 14.6 and about 15.7 ppm, the peaks of aboutequal intensity.
 12. The blend of claim 11 in which the polymercomprising at least about 60 weight percent of units derived frompropylene is further characterized as having a skewness index greaterthan about −1.20.
 13. The blend of claim 11 in which the polymercomprising at least about 60 weight percent of units derived frompropylene is further characterized as having a DSC curve with a T_(me)that remains essentially the same and a T_(max) that shifts to the leftas the amount of comonomer in the copolymer is increased.
 14. The blendof claim 12 in which the polymer comprising at least about 60 weightpercent of units derived from propylene is further characterized ashaving a DSC curve with a T_(me) that remains essentially the same and aT_(max) that shifts to the left as the amount of comonomer in thecopolyiner is increased.
 15. The blend of at least two polymers in whichat least two of the polymers (a) comprise at least about 60 weightpercent of units derived from propylene and at least about 0.1 weightpercent of units derived from a comonoiner selected from the groupconsisting of ethylene and an unsaturated monomer other than ethylene,and (b) are characterized as having ¹³C NMR peaks corresponding to aregio-error at about 14.6 and about 15.7 ppm, the peaks of about equalintensity.
 16. A blend of (A) at least one propylene homopolyinercharacterized as having ¹³C NMR peaks corresponding to a regio-error atabout 14.6 and about 15.7 ppm, the peaks of about equal intensity, and(B) at least one polymer other than a copolymer (1) comprising at leastabout 60 weight percent of units derived from propylene and at leastabout 0.1 weight percent of units derived from a comonomer selected fromthe group consisting of ethylene and an unsaturated monomer other thanethylene and (2) being characterized as having at least one of thefollowing properties: (i) ¹³C NMR. peaks corresponding to a regio-errorat about 14.6 and about 15.7 ppm, the peaks of about equal intensity,(ii) a skewness index, S_(ix), greater than about −1.20, and (iii) a DSCcurve with a T_(me) that remains essentially the same and a T_(max) thatshifts to the left as the amount of comonomer in the copolymer isincreased.
 17. The blend of claim 16 in which the propylene homopolyineris further characterized as having substantially isotactic propylenesequences.
 18. The blend of claim 17 in which the isotactic propylenesequences of the propylene homopolymer have an isotactic triad (nun)measured by ¹³C NMR of greater than about 0.85.
 19. The blend of claim16 in which the polymer of(B) is a propylene/unsaturated monomer otherthan ethylene interpolymer.
 20. The blend of claim 16 in which thepolymer of (B) is a polypropylene other than the propylene homopolymerof (A).
 21. A process for making the copolymer of claim 1, the processcomprising contacting propylene and the unsaturated comonomer underpolymerization conditions with a nonmetallocene, metal-centered,heteroaryl ligand catalyst in combination with at least one activator.22. A process for making an isotactic propylene polymer, the polymer (A)comprising at least about 60 weight percent of units derived frompropylene and at least about 0.1 weight percent of units derived from anunsaturated monomer other than ethylene, and (B) characterized as having¹³C NMR peaks corresponding to a regio-error at about 14.6 and about15.7 ppm, the peaks of about equal intensity, the process comprisingcontacting under polymerization conditions propylene and ethylene with anonmetallocene, metal-centered, heteroaryl ligand catalyst incombination with at least one activator.
 23. The process of claim 22 inwhich the metal component of the catalyst is at least one of hafnium andzirconium.
 24. The process of claim 23 in which the catalyst comprises aligand of the general formula:

wherein R¹ is characterized by the general formula:

where Q¹ and Q⁵ are substituents on the ring other than atom E, with Eselected from the group consisting of carbon and nitrogen, and with atleast one of Q¹ or Q⁵ having at least 2 atoms; q is 1, 2, 3, 4 or 5; Q″is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; T is a bridging group selected from the groupconsisting of —CR²R³— and —SiR²R³— with R² and R³ independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; and J″ is selected from the group consisting ofheteroaryl and substituted heteroaryl.
 25. The process of claim 24conducted under solution polymerization conditions.
 26. The process ofclaim 24 conducted under slurry polymerization conditions.
 27. Theprocess of claim 24 conducted under gas phase polymerization conditions.28. The process of claim 24 in which the unsaturated comonomer is atleast one of a C₄₋₂₀ α-olefin, a C₄₋₂₀ diolefin, a C₈₋₄₀ vinyl aromaticcompound, and a halogen-substituted C₈₋₄₀ vinyl aromatic compound. 29.The process of claim 24 in which the unsaturated comonomer is a C₄₋₁₂α-olefin.
 30. The process of claim 24 in which the unsaturated comonomeris styrene.
 31. A solution phase process for making a high weightaverage molecular weight (M_(w)), narrow molecular weight distribution(MWD) polymer, the polymer comprising at least about 60 weight percentof units derived from propylene and at least about 0.1 weight percent ofunits derived from an unsaturated comonomer other than ethylene andbeing characterized as having ¹³C NMR peaks corresponding to aregion-error at about 14.6 and about 15.7 ppm, the peaks of about equalintensity, the process comprising contacting propylene and theunsaturated comonomer other than ethylene under solution phasepolymerization conditions with a nonmetallocene, metal-centered,heteroaryl ligand catalyst.
 32. The process of claim 31 in which thecatalyst comprises a ligand of the general formula:

wherein R¹ is characterized by the general formula:

where Q¹ and Q⁵ are substituents on the ring other than atom E, with Eselected from the group consisting of carbon and nitrogen, and with atleast one of Q¹ or Q⁵ having at least 2 atoms; q is 1, 2, 3, 4 or 5; Q″is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; T is a bridging group selected from the groupconsisting of —CR²R³— and —SiR²R³— with R² and R³ independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; and J″ is selected from the group consisting ofheteroaryl and substituted heteroaryl.
 33. The process of claim 32 inwhich the metal component of the catalyst is at least one of hafnium andzirconium.
 34. A series reactor process for making a polymer blend, theblend comprising (A) a first component comprising a first copolymer ofpropylene and an unsaturated comonomer other than ethylene, and (B) asecond component comprising at least one of a propylene homopolyiner anda second copolyrner comprising propylene and at least one comonomer ofat least one of ethylene and an unsaturated comonomer other thanethylene, the first and second components different from one another,the process comprising:
 1. Contacting in a first reactor (a) propylene,(b) an unsaturated comonomer other than ethylene, and (c) apolymerization catalyst under polymerization conditions such that thepropylene and the unsaturated comonomer are convened to the copolymer ofthe first component, and (a), (b), (c) and the copolyrner of the firstcomponent forming a reaction mass within the first reactor; 2.Transferring the reaction mass of the first reactor to a second reactor;3. Feeding additional propylene and, optionally, ethylene to the secondreactor;
 4. Contacting within the second reactor under polymerizationconditions the propylene and any optional ethylene fed to the secondreactor with the reaction mass from the first reactor to make at leastone of the polypropylene homopolymer or the second copolymer; and 5.Recovering the blend from the second reactor; with the provisio that ifthe second component either (I) does not comprises a propylenehomopolymer, or (II) it does comprise a propylene homopolymer but thehomopolymer does not exhibit ¹³C NMR peaks corresponding to aregio-error at about 14.6 and about 15.7 ppm, the peaks of about equalintensity, then that at least one of the first and second copolymers arecharacterized as having ¹³C NMR peaks corresponding to a regio-error atabout 14.6 and about 15.7 ppm, the peaks of about equal intensity.
 35. Aseries reactor process for making a polymer blend, the blend comprising(A) a copolymer of propylene and an unsaturated comonomer other thanethylene and being characterized as having ¹³C NMR peaks correspondingto a region-error at about 14.6 and about 15.7 ppm, the peaks of aboutequal intensity, and (B) a propylene homopolymer, the processcomprising: A. Contacting in a first reactor (i) propylene, (ii) theunsaturated comonomer, and (iii) an activated, nonmetallocene,metal-centered, heteroaryl ligand catalyst under polymerizationconditions such that at least about 50 wt % of the propylene andsubstantially all of the unsaturated comonomer are convened to thecopolynier, the propylene, unsaturated comonomer, catalyst, andcopolymer forming a reaction mass within the first reactor; B.Transferring the reaction mass of the first reactor to a second reactor;C. Feeding additional propylene to the second reactor; D. Contactingwithin the second reactor under polymerization conditions the propylenefed to the second reactor with the reaction mass from the first reactorto make the propylene homopolymer; and E. Recovering the blend from thesecond reactor.
 36. The process of claim 35 in which the catalystcomprises a ligand of the general formula:

wherein R¹ is characterized by the general formula:

where Q¹ and Q⁵ are substituents on the ring other than atom E, with Eselected from the group consisting of carbon and nitrogen, and with atleast one of Q¹ or Q⁵ having at least 2 atoms; q is 1, 2, 3, 4 or 5; Q″is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; T is a bridging group selected from the groupconsisting of —CR²R³— and —SiR²R³— with R² and R³ independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; and J″ is selected from the group consisting ofheteroaryl and substituted heteroaryl.
 37. The process of claim 36 inwhich the metal component of the catalyst is at least one of hafnium andzirconium.
 38. A parallel reactor process for making a polymer blend,the blend comprising (A) a first polymer comprising units derived frompropylene and an unsaturated comonomer other than ethylene, and (B) asecond polymer comprising units derived from at least one of propylene,ethylene and an unsaturated comonomer other than ethylene, the first andsecond polymers different from one another, the process comprising: 1.Contacting in a first reactor under polymerization conditions propyleneand an unsaturated comonomer other than ethylene to make the firstpolymer;
 2. Contacting in a second reactor under polymerizationconditions at least one of propylene, ethylene and an unsaturatedcomonomer other than ethylene to make the second polymer;
 3. Recoveringthe first polymer from the first reactor and the second polymer from thesecond reactor; and
 4. Blending the first and second polymers to formthe polymer blend; with the provisio that at least one of the first andsecond polymers comprise either (1) a propylene homopolymer exhibiting¹³C NMR peaks corresponding to a regio-error at about 14.6 and about15.1 ppm, the peaks of about equal intensity, or (2) apropylene/unsaturated comonomer copolymer characterized as having ¹³CNMR peaks corresponding to a regio-error at about 14.6 and about 15.7ppm, the peaks of about equal intensity.
 39. The process of claim 38 inwhich the polymerization conditions include a catalyst comprising aligand of the general formula:

wherein R¹ is characterized by the general formula

where Q¹ and Q⁵ are substituents on the ring other than atom E, with Eselected from the group consisting of carbon and nitrogen, and with atleast one of Q¹ or Q⁵ having at least 2 atoms; q is 1, 2, 3, 4 or 5; Q″is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; T is a bridging group selected from the groupconsisting of —CR²R³— and —SiR²R³— with R² and R³ independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof; and J″ is selected from the group consisting ofheteroaryl and substituted heteroaryl.
 40. The process of claim 39 inwhich the metal component of the catalyst is at least one of hafnium andzirconium.